JP2001510251A - Paper products containing filling materials - Google Patents

Abstract

  (57) [Summary] A composite product having an inorganic network structure polymerized around a cellulosic material and a method for producing the product. One embodiment of the composite product comprises, instead of containing discrete particles of filler particles deposited on or intentionally bound to the cellulosic material, around the cellulosic material: Consisting of and / or around it, a paper product containing a polymerized inorganic network, such as a silica / silicate network. In one embodiment of the method, a mixture comprising a cellulosic material, a Group I metal silicate and a Group II metal base or salt is provided. The mixture is then carbonated to produce a product having a precipitated carbonate filler material and an inorganic network polymerized around the cellulosic material. The product is then shaped into a paper product, where the ash content is significantly higher than a normal paper product, while maintaining suitable strength properties.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to composite products containing fillers, in particular paper products,
Prior to combining the agglomerated filler particles with the cellulosic material and / or polymerized mineral network, the filler is agglomerated with the starch particles, and the present invention relates to a method of making the same.

[0002]

[Prior art]

Paper products are composite products, in which cellulose fibers, especially wood fibers, are the main components. In addition to fibers, many other materials and chemicals have been added to form the desired product. Paper products contain mineral additives, often referred to as fillers, such as clay, calcium carbonate, talc, kaolin, calcium sulfate and titanium dioxide. Paper is mainly made of cellulose fiber web (network structure),
Consists of small amounts of mineral and / or organic fillers. Fillers, as the name implies, have been used to fill the space defined by the cellulose fibers of the web. Fillers also enhance certain paper properties such as opacity, whiteness and printability. Also, other additives such as pigments, dyes, starches, sizing agents and strength enhancing polymers can be used to produce paper with the desired end product properties.

[0003] Cellulose products can be produced more economically using conventional fillers than when using such fillers, primarily due to the cost of the cellulosic material. Traditionally, kaolin clay (hydrated aluminum silicate), chalk, ground limestone and marble, (calcium carbonate), talc (
Hydrous magnesium silicate), gypsum (calcium sulfate) and diatomaceous earth (silicon dioxide) have been used as fillers. Most other fillers are inorganic materials produced synthetically from minerals (e.g. titanium dioxide, synthetic silica, barium sulfate) or regenerated after purification (e.g. limestone-lime-precipitated calcium carbonate) ).

[0004] The fillers used to produce paper products using the methods developed prior to the present invention are subject to cracking of the product as the percentage of fillers used to make the product increases. It results in a decrease in strength properties, such as the length of break (in kilometers, tensile strength divided by the reference weight time 102 according to TAPPI method T494). FIG. 1 illustrates this effect. As shown in FIG.
As the percentage increases, the strength of the paper decreases significantly. Experience has also shown that other undesirable changes occur as the amount of filler used in normal papermaking processes increases.

[0005] Numerous solutions have been proposed and investigated to increase the amount of filler that can be used to make paper products. The usual solution is to combine the filler particles into a fibrous material. The success of this solution has been limited. This is mainly because (1) the fibrous material and the filler are not chemically similar, and (2) the cost of the materials used to manufacture products using this solution is high. . Chemicals, chemical compositions and methods are known for solving the problems associated with increasing filler and reducing cellulosic material in paper products. For example, retention chemistries and compositions are commercially available. These materials have proven satisfactory in solving the problems associated with agglomerating and retaining filler particles in sheets. However, these conventional inventions do not improve the strength of the paper, and therefore do not solve the problem associated with the decrease in the paper strength when the filler content is increased. One possible explanation for this is:
The retention chemistry and composition are good at aggregating the filler particles, but also aggregating the filler onto the fibers themselves. It is believed that paper strength develops primarily as a result of fiber-to-fiber bonding between adjacent fibers. This fiber-to-fiber bond occurs at fiber surfaces that overlap one another. Agglomeration of the filler onto the fibers reduces the surface area of the fibers that are subjected to this inter-fiber bonding, and possibly also reduces the inter-fiber bonding, thereby reducing the strength of the paper product.

[0006] 1. Silica and Silicates as Fillers Silica and silicates are common materials and have been used as fillers, retention aids, buffers, chelating agents and coatings for the manufacture of paper products. . Indeed, World Minerals manufactures a range of products containing calcium silicate to increase bulk, control sticking, and improve printability.
As described above, when a filler or a pigment material is manufactured using silica or silicate materials, even if particles having a large particle size are manufactured at first, the filler particles are not used. Reduce particle size to classical range (0.1-10 microns). For example, in the method for producing paper described in U.S. Pat. No. 4,790,486, when producing a hydrous silicate filler, the slurry is finely pulverized in a wet process to reduce large particles to 1-30 microns. . U.S. Pat. No. 5,030,284 discloses a technique for spray drying a gelled alumina-sulfate composition to produce 1-10 micron particles. Silica and silicates have been used as retention / dehydration aids in making paper. For example, US Pat. No. 5,127,994 describes the use of colloids based on silica. The colloid particles have a particle size of 4-7 nanometers. The improved binder system described in U.S. Pat. No. 4,643,801 comprises three components: cationic starch, anionic polymer and 1-50.
Contains dispersed silica having a particle size of nanometers (0.001-0.05 microns). This system requires these three components and utilizes small dispersed silica. This includes U.S. Pat. Nos. 4,385,961 and 4,38, including binder systems containing colloidal silicic acid and cationic starch.
It seems to be a variant of 8,150.

[0007] Another variant of these retention / dehydration aids is the formation of microgels, which are three-dimensional chain networks of particles having a particle size of 1-2 nanometers. Stabilizing these small colloidal particles prevents further growth and gel formation. See, for example, U.S. Patent Nos. 4,954,220, 5,279,807 and 5,312,595. Neutralizing the alkaline silicate solution produces polysilicic acid (from polymerizable anions), which polymerizes to form a microgel of three-dimensional aggregates of very small particles of polysilicic acid .
The formation of the polysilicate microgel is initiated by adding an acidic material (aluminum sulfate, sodium stannate, sodium orthoborate decahydrate, acidic ion exchange resin, sodium aluminate, etc.). Gelation (polymerization) by this "initiator"
The process is started and stopped before the solution has completely gelled. This process is performed independently of the papermaking process. Then any other retention / dehydration additives are added to the system. Referring to FIG. 2, the polymerization behavior of silica is shown. Polysilicic acid microgels have been found to be good retention / dehydration aids when combined with water-soluble cationic polymers.

According to the disclosure of US Patent No. 5,240,561 to Kaliski, a microgel similarly formed from a solution of an alkali silicate and a second aqueous solution of sodium aluminate or sodium zincate is used. . The Kaliszky patent relates to a method of making paper and teaches forming microgels (in furnish) in situ. However, the microgels he discloses are described as transient, are chemically reactive, are subcolloidal sodium-silica-aluminates or similar microgels, and produce colloidal particles ( Prior to the Tyndal effect), it must be crosslinked with divalent and / or polyvalent inorganic salts (such as calcium chloride). Due to this cross-linking, the gelling process (polymerization reaction) stops immediately and precipitates as a calcium cross-linked microgel. Kaliski shows that this procedure is used for papermaking as a new agglomeration mechanism, in which mitrogel precipitates, causing all particles present in the papermaking furnish to solidify and agglomerate.
Thus, the Kaliszky patent is a variation of the previously described patent for retention / dehydration aids, but which is implemented in situ. In the Kaliszky patent, a specific order of addition is required to stop the polymerization at the stage of subcolloid growth (sodium silicate second, sodium aluminate second, calcium chloride third). . U.S. Pat. Nos. 5,116,418 and 5,2 of Kaliszky
No. 79,663 discusses using this aggregation technique to produce a dye. U.S. Pat. No. 5,378,399 to Kaliski discusses the formation of functionally complex microgels.

[0009]

[Problems to be solved by the invention]

The patents mentioned above relate to colloidal particles and / or microgels and do not provide evidence that a large three-dimensional inorganic network has formed around the fibers. The initial particles or microgels are very small (typically 1-50 nanometers and less than 100 nanometers or 0.1 micron), and larger particles are actually Brings disadvantages.
The concentration of silica / silicate in the papermaking process and subsequent dilution of these materials will preclude the formation of a larger mineral network.

[0010] Some literature teaches that larger inorganic product networks are not desirable for the production of paper products. For example, U.S. Pat. No. 3,720,531 states that "as is well known, the products obtained by simple neutralization of alkali silicates are used as absorbents and catalysts. Although useful, however this (plus enhancement) can not "used as a dye. A similar statement is made by S.M. N
. Ivanov and V.I. V. "Preparation of artificial silicate filler" by Kuznetsky
In an article entitled, "As is well known, during the treatment of water glass (sodium silicate) with a solution of a salt of an acid or a transition metal under normal conditions, a gel forms, which, as a result of its structure and properties, , it is not possible to work as a filler "(emphasis was added). Japanese Unexamined Patent Publication No. Hei 5-239797 discusses the use of calcium silicate to produce a fire resistant paper, and U.S. Pat. No. 5,372,678 discloses the use of ordinary fourdrinier. Rather, it discloses that a molding / pressing operation is performed to produce a fireboard bonded with calcium hydrogen silicate.

[0011] 2. Pre-agglomeration of Filler Particles Also, methods have been developed to increase the loading of the filler while increasing the strength of the paper. One such technique is to pre-agglomerate the filler particles before adding the filler particles to the cellulosic fibrous material. This pre-agglomerated filler agglomerate is better retained by the web created by the cellulosic fibrous material and does not agglomerate onto the fibers. This increases the surface area of the fibers available for fiber-to-fiber bonding and improves the strength of the paper product. The method for pre-aggregating the filler particles is generally the wet end of the papermaking process.
It is based on the same chemicals as the holding material applied to. This includes charge neutralization and the use of retention chemicals to crosslink between the filler particles.
Similarly charged filler particles repel each other. Charge neutralization involves neutralizing the charge on the particles to remove this repulsion, thereby aggregating the particles. Chemicals used in this process include cationic starch, high molecular weight cationic or non-ionic polymers, or a combination of cationic starch and polymer. Cationic starch is commonly used in the wet part of papermaking processes to agglomerate fiber fines, since cationic starch contains a positive charge that can cause the negatively charged pigment particles to agglomerate.

Although it is advantageous to pre-agglomerate the filler particles, there are disadvantages. One disadvantage is that it has proven difficult to control the size of the agglomerates produced by the agglomeration process. This results in the formation of large agglomerates, which may appear as visible defects in the final paper product, or which may form too small agglomerates and retention aids to retain the agglomerates in the sheet May need to be used. As mentioned above, starch has been used to pre-agglomerate the filler particles, and some of these inventions have been patented. In these inventions, a starch polymer is used to agglomerate the filler particles, and agglomerates of the desired size are produced, for example, by subjecting the agglomerates to high shear forces through complex process designs. ing. One example of a method for agglomerating filler particles using a starch polymer is US Pat. No. 4,151,187 to Richard Davidson.

Although starch has been used in the production of paper products prior to the present invention, one of ordinary skill in the papermaking art is that the use of cationic starch in the wet part of the papermaking process will result in the formation of filler fines and pigment particles. The retention of has been improved. In addition, most starches have been chemically modified from their native form prior to use as flocculants. For example, corn starch is often chemically treated, even if it is ethylated,
It alters its naturally occurring chemical structure. The modified starch is then cooked, which causes the starch to degrade and dissolve in water. Then
A starch film forms on the fibers. Also, the starch is cationic, that is, it provides a material that is chemically modified to provide a positive charge, thereby attracting the starch electrostatically to the fiber portion of the negatively charged paper. Can be Modification and cationization of starch increases the number of processing steps and increases the cost of the overall papermaking process.

[0014]

[Means for solving the problem]

The present invention, in one aspect, provides a new solution to the filler concentration-strength problem shown in FIG. 1 and further represents a radically different solution with respect to the composition, structure and formation of cellulosic products. It is. Past attempts to overcome the limitations of strength reduction of paper products made with fillers have been limited by the basic principle that strength is derived primarily from the bonding of fibers. Prior to the present invention, those having ordinary skill in the papermaking arts generally did not find it beneficial to bond filler particles together during the production of paper products. This is because this reduces the number of distant filler particles and reduces both opacity and bulk of the product.

The present invention departs from the concept of relying solely on bonding fibers together to obtain sufficient strength in a cellulosic product. The product of the present invention is not merely a fibrous mat with a filler, but rather a composite structure, in which the filler particles contained by the composite bond to each other (and possibly also to the cellulosic material). ), And an inorganic network structure is produced by a polymerization reaction around cellulose. The result is a new composite product with different properties than regular paper products. One reason for this is that the properties of the composite product, e.g., strength, stiffness, opacity, printability, etc., are dependent on the interconnecting of the fibers, generally the fillers polymerized at least partially in the presence of the fibers. This is due to the network, and in some embodiments, the network of the filler polymerized around the fiber, and possibly the bond between the network and the fiber.

The specific example of the composite product of the present invention differs from ordinary paper products in that the process used to produce the product (referred to herein as the Ca-FLOCC process) is intended to provide a fiber To produce a polymerized inorganic network, such as a silica / silicate network, around the material, throughout the fiber material and / or surrounding the fiber material. Around it is called "generating an inorganic network"). This is in contrast to the usual method of depositing separated filler material particles on a cellulosic material or binding such filler particles to the cellulosic material. In other embodiments, the generation of the network begins outside the presence of the fiber and then continues after binding with the fiber (here, Mg
-FLOCC and Si-FLOCC methods).

One difference between the composite product of the present invention and a normal paper product is shown in FIGS.
Scanning electron micrographs of paper products produced by the present invention, particularly by the Ca-FLOCC method, are clearly distinguishable from paper products produced using the conventional method, and furthermore by the Ca-FLOCC method, and to some extent Are Mg-FLOCC method and Si-FLO
It has been shown that the CC method produces an inorganic network around the fibers. Scanning electron micrographs of the ash of cellulosic products produced by the Ca-FLOCC process (i.e., primarily the combustion products of the materials added to produce non-cellulose products) are similar to the still polymerized networks. This is in contrast to the more brittle ash that results from products in which the filler particles are volumeized or bound on the cellulosic material, as in conventional paper products. Fig. 7-10
See

The products of the present invention are usually stronger than regular paper products having the same ash content. On the other hand, while achieving this, the filler content is significantly increased relative to the filler material normally found in paper products made to distribute or combine the individual filler product particles on the cellulosic material. Is increasing. The invention also relates to a method for producing a composite product. The method is
It consists, at least in part, in polymerizing the inorganic network in the presence of the cellulose fibers or around the cellulose fraction. This Si-FLOCC
The simplest and easiest solution for producing a product by a process involves acidifying, for example, by adding carbon dioxide to a Group I metal silicate material and then adding this material to cellulose. . Other solutions for polymerizing the mineral network include cellulose materials, silicates of Group I metals, especially sodium silicate, and bases or salts of Group II metals, especially calcium and magnesium salts (
This example gives a mixture containing calcium oxide and magnesium oxide, and calcium hydroxide and magnesium hydroxide). The mixture is then acidified, and possibly co-carbonated, to give a product comprising precipitated carbonate filler material and a polymerized inorganic network around the cellulosic material. This product can be formed into a conventional cellulosic product, such as a paper product. Carbonation of the mixture can be achieved by combining the mixture with carbon dioxide, but other conventional methods for carbonating aqueous mixtures are also available.

The mixture typically comprises (1) about 40 to about 60% by weight of a cellulosic material (unless otherwise noted, all percentage ratios described herein are dry in a stock oven) (By weight to solids), especially delignified cellulose, (2) about 0.
5 to about 20% of a Group I metal silicate, especially sodium silicate, and (3) about 0%
. 5 to about 45% of a salt of a Group II metal, for example calcium oxide, wherein the content of the Group II metal salt is generally equal to the content of said silicate, more typically Greater than. The mixture is then shaped to obtain a paper product. The mixture may also contain other materials commonly used in the production of paper products, such as fillers such as precipitated calcium carbonate, starch, retention aids, brighteners, insecticides, The material is selected from, but not limited to, the group consisting of sizing agents, pigments (titanium oxide, clay, talc, etc.) and mixtures thereof.

The present method offers several advantages over conventional methods. For example, higher filler contents can be utilized in the production of the product, while at the same time reducing costs. Also, precipitated filler materials, such as precipitated calcium carbonate, can be produced in situ during the production of the product, thereby using good quality filler and uniform distribution throughout the product. And possibly compensation for impregnation into the mineral network. The present invention also provides a method for pre-agglomerating filler particles useful in the manufacture of paper products. In the method, a starch is provided, the starch is processed to form starch granules, and the filler particles are mixed with the starch granules to form a filler particle-starch agglomerate. The starch is generally selected from the group consisting of legume starch, potato starch, corn starch and mixtures thereof, and is preferably pea starch. In the process of treating starch, typically an aqueous starch dispersion containing about 1 to about 10% by weight of starch is provided and the dispersion is treated at a temperature of about 60 ° C to about 120 ° C, preferably about 7 ° C.
Heat to a temperature between 0 ° C and about 90 ° C. The average particle size of the starch granules is typically from 15 μm to about 150 μm, preferably from about 40 μm to about 70 μm.

[0021] In the method for producing a paper product provided by the present invention, the starch particles are treated to form starch granules, and the starch granules are mixed with the filler particles to form a filler particle-starch aggregate. Pre-agglomerating filler particles useful in the manufacture of paper products by forming; preparing a cellulose fraction; simultaneously with or subsequent to binding the filler particle-starch aggregates to said cellulose fraction. An inorganic network is formed around the cellulose fraction.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention relates to the manufacture of paper products that overcome the disadvantages discussed in the "Background of the Invention" section. In the present invention, a polymerized inorganic network is formed around the fibers and / or the filler particles are pre-agglomerated with the starch granules prior to bonding the agglomerated filler particles with the fiber fines. Various embodiments of a method of manufacturing a paper product having a polymerized inorganic network structure and various embodiments of a product manufactured by the method will be described later. Various embodiments of a method of making a paper product by pre-agglomerating filler particles with starch granules and various embodiments of a product made by the method are described below. In this example, not only working embodiments of these methods and products, but also the pre-agglomeration of the filler particles with the starch granules and the formation of an inorganic network around the fiber fines. Working embodiments of paper products produced by both parties are also described above.

I. General Papermaking Process General papermaking processes are known in the art. The following summarizes certain embodiments of a typical papermaking process that will provide an overview of the method to assist in explaining the subsequent features of the invention. Although FIG. 11 is a schematic diagram of a particular papermaking process 10, it should be understood that the present invention may be implemented in papermaking processes that vary from this illustrated process. Looking at FIG. 11 from left to right, the papermaking process 10
Starts with a stock slurry, which contains cellulose fibers in water, e.g.
A thin suspension containing 10% concentration. This stock is shown in FIG.
Hold in the holding tank designated as 2. This stock is transferred from the HD tank 12
Feed through a refining chest 14 into a series of primary refining machines 16. With this primary refining machine 16, the fibers are subjected to mechanical force and hydraulic pressure to change the fiber properties. The stock is then fed into a compounding chest 18 where the stock is compounded with different types of fibers and / or different types of drugs, chemicals and fillers. The resulting stock is then fed through a mechanical chest 20 into a series of secondary refiners 22. The secondary refining machine 22 subjects the fibers to mechanical and hydraulic pressure to further alter the properties of the fibers. Altering the fiber properties in the primary and secondary refiners 16 and 22 includes breaking some of the intra-fiber bonds and allowing water to penetrate into the fibers.

[0024] After this secondary refining process, to ensure uniform dispersion in the system, the stock is
It is supplied into a stereotactic tank called "stuff box 24". In the stuff box 24, starch and sizing can be added to the stock. Starch acts as an inter-fiber binder, while sizing agents act to remove moisture from the finished paper product. The stock enters the machine silo 26 from the staff box 24 and is diluted. After the stock exits silo 26, the filler can be introduced into the stock. In the drawing shown, the filler is precipitated calcium carbonate (PCC), which is referred to as PCC.
It is fed from a tank 28 into the stock. The filler fills gaps in the web of cellulosic fibers. The stock is then fed by a primary cleaner feed pump into a series of centrifugal cleaners 32, from where it is fed into a decurator deaerator 34 where air entrained by the stock is removed. The fan pump 30 provides a screen 36 to remove foreign matter and coarse, irregular, or unseparated fibers from the stock. A retention aid can be added before or after the stock is fed through the pump 30. Fillers, fibers, fines, additives (size, starch), etc. are retained by the retention aid in the web of cellulose fibers while the dilute stock is passed along the porous conveyor of the paper machine.

Next, the stock is supplied to a paper machine. The stock first enters the headbox 38, which pressurizes the stock and then expels the sheet of stock into a continuous porous conveyor belt. While the sheet is moved by the conveyor belt, suction is applied by a machine to remove water from the fiber web. The sheet is then conveyed through a wet press 40, thereby further removing water from the sheet and bringing the fibers together. The sheet is then conveyed through a series of heated rollers (dryer 42) to evaporate most of the water remaining by the lier,
This causes the formation of interfiber bonds inside the sheet. After the dryer 42, the sheet travels past a sieve press 44, and a size press sizing the surface of the sheet ("Sai zinc" means adding a sizing agent to the surface of the sheet), and the starch is sheeted. To bind the filler, the filler folded up from the surface of the sheet and any fibers downward, and further add inorganics or fillers such as salts. The sheet is then conveyed through another series of heating rollers, an afterdryer 46, where the moisture remaining from the sheet is evaporated. The dried sheet is calendered through a series of roll nips or calendar stacks 48 to reduce sheet thickness and create a smooth sheet surface. The sheet then passes through a reel 50 and is wound up by a winder 52 on a paper roll.

II Ca-FLOCC, Ng-FLOCC and Si-FLOCC Paper Products A General Methods and Processes for Producing Composite FLOCC Products There is a general method. (1) A mixture containing a silicate of a Group I metal is acidified in the presence of a base or a salt of a Group II metal. (2) a mixture of silicates of group I metals, possibly I
Carbonation in the presence of a base or salt of a Group I metal. (3) Use a cement-like material. At present, the first and second methods are preferred, and working examples of handsheet production and papermaking tests for both of these methods are provided below. To carry out the general method, (1) select the appropriate drug, (2) produce an aqueous mixture containing most if not all of the desired drug, and (3) acidify the mixture, Possibly carbonated, (4) if necessary, adding other materials commonly used to produce paper products, and (5) the mixture after sufficient curing time to obtain the desired product properties. From paper products. Each of these steps is discussed in further detail below.

1. Drug Selection a. Cellulose material Cellulose material, in terms of weight percent, is a major component of the composite product,
The cellulosic material used may vary. In the working example of the present invention, a mixture containing hardwood and softwood was used. However, the present invention can be practiced with all cellulosic materials commonly used to produce paper products, whether new, recycled, chemical, mechanical, or lignin-containing pulp. You should understand what you can do. The amount of cellulosic material added is generally the balance of the composite product after considering the additional desired materials used to produce the particular product.

B. Inorganic network structural material Second material (or materials) used to make the product of the present invention
Is a material (or a plurality of types of materials) for forming an inorganic network structure. A number of mineral networks appear to be useful, and the present invention relates to all such mineral networks. In the working example of the method, a paper product having an inorganic network containing silica, silicate and aluminosilicate was produced. These materials are discussed in further detail below, along with possible chemical laws for the formation of an inorganic network. Other examples of inorganic networks useful in forming the products of the present invention include boron oxide, aluminum oxide, silicophosphate, silicoaluminophosphate and mixtures thereof. The silicate network is generally produced by the present method by treating a mixture containing a Group I metal silicate, especially sodium silicate. Aluminosilicates are formed by using a silicate of a Group I metal and reacting the silicate material with an aluminum compound such as aluminum sulfate (alum). The production of a composite product containing an aluminosilicate will be further described with reference to FIG.

[0029] The amount of mineral network produced for the composite product is typically specified relative to the amount of starting agent added to make the product. This inorganic network is generally less expensive than cellulosic materials. As a result, the portion of the composite product derived from the inorganic network should be as high as possible without sacrificing the desired properties of the composite product. This quantity depends on the quantity of product to be produced. By way of example only, at present, it is believed that the inorganic network precursor material to be added may be from about 0.1-% to about 60%, again based on the oven dried solids weight of the composite. Should preferably be about 1
%-About 40%, more preferably about 2%-about 20%.

The amount of a particular material added to the composite product can also be specified relative to the proportion of ash produced by burning the paper product. Cellulose and other organic materials for papermaking are:
On combustion, it produces gaseous products, mainly carbon dioxide and water, but with inorganic additives (
The products of combustion of the pigments and fillers remain, producing ash. As a result, the amount of inorganic material other than cellulose that forms the present composite product can be specified as a percentage ratio of the amount of ash generated by combustion of the present cellulose product. The total ash content of products made according to the present invention is in the range of about 0.1% to about 60%, typically about 1%.
To about 40%, preferably from about 2% to about 35%.
The amount of this ash contributed by the mineral network is from about 1% to about 100%. At present, there are three types of compositions and methods of treating these compositions, Ca-FLOCC, Mg-FLOCC, and Si-FLOCC methods for producing an inorganic network structure. Each of these will be described separately.

I. Ca-FLOCC Method The Ca-FLOCC method is the primary method for producing an inorganic network around a fiber by completely polymerizing the inorganic network in the presence of the fiber. Compositions which may be useful in performing the Ca-FLOCC process include sources of Group II metals, especially Ca ²⁺ , especially CaO, and sources of silicates of Group I metals, such as sodium silicate, potassium silicate And lithium silicate, especially sodium silicate, and fibers. Aluminum sources such as aluminum nitrate, aluminum acetate, aluminum halide salts and aluminum sulfate can be added to form aluminosilicates. This mixture is then combined with the cellulose and acidified. The presently preferred method for acidifying the silicate is to add dry ice and carbonate the mixture, or bubbling carbon dioxide gas through the aqueous mixture. The relative amounts of these materials are as follows: 40-95%, preferably 6
0-80% fiber: 0.5-35%, preferably about 2% to about 15% sodium silicate: 0.5-35%, preferably about 2% to about 15% calcium hydroxide. Add a sufficient amount of carbon dioxide to obtain a pH of about 7 to about 9, preferably about 8.0.
Get.

Ii. Mg-FLOCC Process Compositions that are found to be useful for forming paper products by the Mg-FLOCC process include a source of a Group II metal, preferably Mg2 ⁺ , such as MgO, a Group I metal,
It consists of an aqueous composition, for example of a sodium, potassium or lithium silicate source, in particular sodium silicate. Aluminosilicates can be formed by adding also aluminum compounds such as aluminum sulfate.
The composition is then acidified, preferably by adding gaseous carbon dioxide. In contrast to the Ca-FLOCC method, the polymerization or gelling of the reaction mixture can be performed partially outside the presence of the fibers. However, the reaction mixture typically continues the polymerization reaction in the presence of the fiber. The relative amounts of the plurality of components used in the composition for the Mg-FLOCC method are typically as follows with respect to the amount of the group I metal silicate. The amount of Group I metal silicate is from about 1% to about 7%, preferably about 3.5%, as sodium silicate, based on the amount of water added. The Mg ²⁺ compound is from about 0.05% to about 10% by weight, preferably from about 0.25% to about 0.3% by weight. If aluminum is desired, then an aluminum source (e.g., aluminum sulfate) may be added in an amount greater than 0 grams and about 0.
Up to 4 grams should be added, with about 0.15 to about 0.2 grams of the aluminum source being preferred. The mixture is then acidified, preferably by carbonation, to a pH of about 7 to 9, preferably about 7-8.

Iii. Si-FLOCC Process Compositions that appear to be useful for forming paper products by the Si-FLOCC process contain a source of silicate, such as potassium silicate, sodium silicate or lithium silicate, especially sodium silicate. Consists of an aqueous composition. Aluminum compounds such as aluminum sulphate can likewise be added to form aluminum silicates. The composition is then acidified to a pH of about 7-9, preferably about 7-8, preferably by the addition of gaseous carbon dioxide. The amount of silicate used can vary. However, it is currently contemplated that about 1% to about 7% sodium silicate, preferably about 2% to about 3% sodium silicate, will provide an amount of material suitable for performing the Si-FLOCC process. It is. Further, if an aluminum compound such as aluminum sulfate is added, then about 0 to about 0.4 grams of aluminum compound (aluminum sulfate) is used per gram of silicate.

C. Fillers Filler materials commonly used in forming paper products can also be used to form the composite products of the present invention. Any known or later developed filler useful for the production of paper products can also be generally used in the manufacture of composite products according to the present invention. A currently preferred filler is calcium carbonate, especially precipitated calcium carbonate (PCC). Precipitated calcium carbonate can be added directly to the composite product during formation of the composite product using commercially available precipitated calcium carbonate, or the composite can be added in situ, i.e., in the presence of a cellulosic material. Precipitated calcium carbonate can be produced during the production of the product, or both. The amount of filler used to make the composite product may also vary. In the working example of the present invention, about 1% to about 50% of filler, especially precipitated calcium carbonate, is added, based on the oven dried solids weight of the composite product, typically about 3%.
% To about 35%, preferably about 5% to about 30%.

D. Group II Metal Bases or Salts As noted above, Ca-FLOCC and Mg-FLOCC processes typically involve bases and salts of Group II metals, especially calcium bases such as calcium oxide (CaO) and magnesium oxide. And chemically equivalent materials such as Ca (OH) ₂ and Mg (OH) ₂ . Such materials may be added for several reasons, such as the formation of a mineral network with a Group II metal counterion from a Group I metal silicate reagent, or the in situ formation of a filler such as PCC. ing. A currently preferred solution is to add a base or salt of a Group II metal to form the inorganic network and the filler in situ, and to add a commercially available filler such as commercially available PCC. The amount of Group II metal base or salt added to the working examples of the present invention, depending on the desired result, is at least small relative to the amount of Group I metal silicate used, Equivalent and abundant.

E. Other Additives Other materials commonly used to make cellulosic products can also be used to make the composite products of the present invention. Examples of such materials include starch, retention aids, insecticides, fungicides, brighteners, sizing agents, pigments, dyes, strength enhancing polymers, aluminum sulfate, other fillers and pigments (titanium oxide, clay). , Talc, etc.) and mixtures thereof, but are not limited thereto. These materials are added in predetermined amounts to improve certain properties of the cellulosic product, and this amount determines the best amount for the production of the particular product.

In the working example of paper produced by this method, both cationic and anionic retention systems are often included. For example, cationic “percol 175”, anionic “
A number of retention systems are used, including "percol122LE", "Organopol 21", "Hydrocol O" and mixtures thereof. Currently, preferred retention systems include "Organo
pol 21 "and" Hydrocol O ". Sufficient amounts of these materials are added to improve the retention of fillers and other materials for the manufacture of the product. According to current thinking, "Hy from about 0 pounds / ton to about 16 pounds / ton.
drocol O ", preferably" Hydrocol O "of about 8 pounds / ton, and about 0.05
Working examples of paper products are provided by "Organopol 21" from pounds / ton to about 2 pounds / ton, preferably "Organopol 21" at about 0.4 pounds / ton.

[0038] 2. Production of aqueous mixture Once the appropriate drugs have been selected, the next step is to select some of these drugs,
Or to produce an aqueous mixture containing everything. Currently preferred methods include (1) about 0.1% to about 20%, typically about 1% to about 16%.
%, Preferably from about 2% to about 12%, more preferably from about 2.5% to about 11%, containing a cellulosic material; (2) usually added later in all examples; Contains filler material such as PCC (although fillers can also be added later); and (3) Ca-FLOCC method and Mg-FLOCC as needed
An aqueous mixture is formed which contains the base or salt of the formal Group II metal. This mixture is then stirred to obtain a well-mixed composition. Thereafter, an aqueous solution containing the silicate of the Group I metal is added to this aqueous mixture with stirring.

D. Acidification of the mixture, preferably carbonation The next general step is to acidify the mixture, preferably carbonation. It should be noted that carbonation of the mixture is essentially a specific example of acidification of the mixture. This is because the addition of a carbonating agent into an aqueous system will either induce the addition of the acid or result in the generation of such an acid in situ.

The carbonation of the mixture can be carried out by various methods, for example, by adding carbonic acid or dry ice. The currently preferred carbonation method is to bubble the mixture with carbon dioxide. This produces carbonic acid, which then reacts with the components of the mixture to produce a silica / silicate network. In the working example of the present invention,
The mixture was carbonated by fitting the gas diffusion tube to a gas cylinder containing carbon dioxide. See "Description of continuous processing equipment" below. The diffusion tube is inserted into the aqueous mixture. Carbon dioxide gas is introduced through the diffusion tube into the mixture at a pressure of about 0.5-80 psi. By continuing the carbonation step for a sufficiently long period of time, the pH is lowered from an initial pH of about 10-12 to a final pH of about 7-9.

[0041] 4. Production of Products Having an Inorganic Network Other Than a Silica / Silicate Network Each step of the general process described above involves the steps
It should be understood that it is particularly relevant to the production of composite products by CC and Si-FLOCC processes. If a different mineral network is used to produce the product, the steps of these methods will vary. For example, if the inorganic network is an aluminosilicate network, then the agent containing aluminum, e.g., aluminum sulfate, is also less in weight percentage than the agent comprising a Group I metal silicate, Alternatively, add in an equal amount or in excess. It is preferred that the aluminum sulphate is presently low in agent comprising a Group I metal silicate for excessive strength. See Example 3.

[0042] 5. Curing Time Without limiting the invention to a single operating principle, it is presently contemplated that desirable properties in the present composite product result, at least in part, from the formation of an inorganic network. Some time is required to complete to produce a sufficient amount of mineral network to provide a composite product with the desired properties, such as relatively high filler loading and suitable breaking length. It is.

The time required to produce the composite product obviously depends primarily on the time required to produce the mineral network, but is referred to herein as the "cure" time. This cure time can vary depending on a number of factors. Factors include the composition of the inorganic network, the state in which the network is formed, the degree of the inorganic network that must be generated to provide the desired product properties, pH, temperature, stirring speed, and the like. Is not limited. By way of example only, and as currently contemplated, a Ca-FLOCC product of the present invention may be used for from about 1 to about 50 hours, typically
It can be produced using a cure time of about 5 to about 45 hours, preferably about 10 to about 45 hours. However, it should be understood that the longest cure time is likely to be determined for business reasons. That is, there is a problem of business cost of waiting for a longer time than the above-mentioned time. On the other hand, the shortest cure time is more dependent on whether a sufficient amount of the inorganic network is formed. And, the polymerization reaction process (gelling) process does not stop at the sub-colloid stage, but rather can proceed until an inorganic network is formed around the fibrous material.

When performing the Mg-FLOCC and Si-FLOCC methods, the formation of the composition can be initiated outside the presence of the fibers. This polymerization reaction is started by acidification. If the acidified composition is added to the fibers too early, the resulting paper product will not have the desired properties. However, at the concentrations described above, compositions according to the Mg-FLOCC and Si-FLOCC methods are formed and then combined with the cellulose after storage for at least several days. Thus, it appears that compositions according to the Mg-FLOCC and Si-FLOCC methods should be cured for longer than 15 minutes, preferably for as long as about 30 minutes, but after this time the Mg-FLOCC
And the time for the Si-FLOCC composition to be combined with the cellulose can vary significantly.

6 Production of Cellulose Product The next step is to produce the cellulosic product using conventional means, for example using a paper machine. In the working example of the paper product manufactured according to the present invention, both a laboratory handrailing device and an experimental scale mechanical papermaking device were used. Further details regarding the generation of paper sheets are given in the examples. The following section describes an example of an apparatus useful for continuously producing a FLOCC composition.

B. Apparatus for Continuously Generating Inorganic Material FIG. 12 is a block diagram of an apparatus for continuously generating a gelling product called FLOCC, which is sufficient as a filler in the above-mentioned fiber slurry. Preferably, a silicate solution and an aluminum sulfate solution are fed by a silicate source 100 and an aluminum sulfate source 102, respectively, into a mixer 104, where the solutions are mixed and a uniform reaction mixture is formed. obtain. Alternatively, the reaction mixture may be free of the aluminum sulfate solution and contain a silicate solution. Next, carbon dioxide is diffused from the carbon dioxide gas source 108 into the reaction mixture by the carbon dioxide treatment device 106. The reaction mixture then passes through a curing device 110 where the mixture polymerizes, crosslinks, and forms a gel. Next, the gelled FLOCC
Is fed into the fiber slurry on the suction side of the fan pump of the paper machine (see fan pump 30 in the schematic diagram of the paper machine in FIG. 11).

FIG. 13 shows a more commercially possible embodiment of the device 200 in more detail in schematic form. The apparatus 200 contains alternating two chemicals that make up the silicate source (see silicate source 100 in FIG. 12), which is preferably TO
TE 202, 204. Pumps 214, 2 by motors 206, 208
Powering 16, pump 214 pumps silicate out of TOTE 202 and pump 216 pumps out other chemicals from TOTE 204. In a possible commercial embodiment, the motors 206, 208 are powered by Waukesh.
1 hp motor available from a). Motors (indicated as M throughout the drawing) 206, 208 are controlled by liquid flow rate instruction controllers 210, 212 (referred to as FFIC). Preferably, the ratio of the flow from pump 214 to the flow from pump 216 is constant, whether they are pumping solids or liquids, thereby maintaining the composition of the silicate mixture constant. You. Also, preferably, the pumps 214-216 do not pulsate during use. In the working example of the present invention, pumps 214 and 216 are 500 series pumps available from Moyno, a branch of Robbins and Meyer Company, Springfield, Ohio. Pumps 214, 216 are 1000 series pumps available from Moino. In a possible commercial embodiment, the ponges 214, 216 are Waukesha positive displacement pumps. The two types of chemical substances are mixed at a fixed ratio or ratio by these two types of pumps 214 and 216. In an embodiment in which Mg-FLOCC is generated by device 200, these two chemicals are magnesium oxide (MgO) and sodium silicate. Alternatively, in an embodiment where the Si-FLOCC is generated by the device 200, one type of chemical may be introduced and only one type of pump is required.

In a commercially feasible embodiment for producing Mg-FLOCC by the apparatus 200, silicate and MgO are supplied from TOTE 202, 204 via conduit 2, respectively.
20, 222, through the premixer 224 and into the premix tank 218. The conduits used to conduct the material between the components of the device 200 include:
Hereinafter, it is called a conduit. In a commercially feasible embodiment, each conduit 220, 22
2 has flow indicators 226, 228 (labeled FI throughout the drawing) to indicate the flow rate of silicate into the premix tank 218. Each conduit 220,
222 preferably comprises a pressure relief valve (not shown). The reason why it is preferable to provide this pressure relief valve is that if a blockage occurs, the pumps 214, 2
16 may cause one of the lines to burst. In the premixer 224, the silicate and the MgO are mixed, thereby suspending the MgO in the silicate. Premixer 224 may be a “Komax” static pressure mixer.

In a commercially feasible embodiment, the premix tank 218 includes a level transducer 230 (denoted LT in the drawings). The liquid level transducer generates a signal to a liquid level indicating controller 232 (denoted LIC), which indicates the liquid level of the premix tank 218. The silicate solution is stirred by the stirrer 234 in the premix tank 218 to keep the solution homogeneous and keep the MgO in suspension. The agitator 234 preferably has the ability to agitate a viscous solution of 100-200 cps (centipoise). In a commercially available embodiment, the stirrer 234 is a "Lightnin model XJ-30 Heavy Duty Mixer".

Water can also be fed into the premixer 224 to ensure that the solution retains its desired composition percentage ratio, which is critical to proper operation. Water is generated from the millwater source 236. A water channel 238 extends from the millwater source 236 and includes a variable valve 240 (indicated by a valve symbol coupled to a closed semicircle in the figure). This changes the flow of water in the channel. The water channel 238 further includes a magnetic flow meter 242 (denoted by FE), a flow transmitter 244 (denoted by FT), and a liquid flow rate instruction control device 246 (denoted by FIC) for indicating the flow of water flowing through the water channel. I have. The silicate mixture flows out of the bottom of the premix tank 218, flows through line 252, and flows into pump 258. Dehydration valve 256 (the dehydration valve and other valves
It is typically closed during use, so it is indicated by a dark valve symbol)
Close to premix tank 218 is fluidly coupled to line 252. Also,
Line 252 is provided with a shutoff valve 258 (the shutoff valve and other valves that are typically open during use are indicated by bright valve symbols).

In the working example of the present invention, the tank is supplied to pump 254 without using the pump and premix tank described above. This tank in the present working example is provided with a stirrer, and is provided with a pipeline flowing from the tank to the pump 254. The pump 254 is driven by the variable speed motor 260. The motor 260 is preferably a larger motor and the flow indication controller 262 (FIC)
Is controlled by Pump 254 feeds the silicate mixture through line 270 into in-line mixer 272 (see mixer 104 in FIG. 12). Preferably, the pump 254 pumps at the same rate, whether solid or liquid. Also, the pump 254 preferably does not pulsate during use. Also, in a working example, pump 254 may be a 500 series pump available from Moino. However, the pump 254 may be a 1000 series pump available from Moino. In the commercially available embodiment shown in FIG. 13, pump 254 is preferably a Walkersha displacement pump. Also, in a commercially feasible embodiment, a line 270 between the pump 254 and the in-line mixer 272 has a flow indicator 274 and a non-return valve 276 ( (Indicated by a valve symbol in the drawing, with a line extending in the direction of flow).

The solution or mixture is fed into pump 278. Preferably, the solution contains aluminum sulfate. Preferably, pump 278 pumps at the same rate, whether solid or liquid. In a working example, the pump 278 is a Bellavaristaric pump. However, the pump 278 is a 500 available from Moino.
It may be a series pump, or a 1000 series pump available from Moino, or certain other pumps having the desired characteristics. In a commercially available embodiment, pump 278 may be a Walkersha displacement pump. The pump 278 is driven by a motor 280, which is controlled by a flow rate instruction controller 282 (FIC). Motor 280 may be of the same type as motors 206, 208, 260 described above, but is preferably a 1 hp motor. Pump 278 pumps the solution or mixture through line 284 into in-line mixer 272 where it mixes with the silicate mixture. The reason is that the ratio between the flow of the pump 254 and the flow of the pump 278 is important for accurately maintaining the composition in the resulting mixture.
In the working example, an aluminum sulfate source (see FIG. 12: aluminum sulfate source 10)
2) is a tank for supplying into a pump. In a commercially feasible embodiment, the aluminum sulfate source (see FIG. 12, aluminum sulfate source 102) comprises:
TOTE286. Also, in a commercially feasible embodiment, the pump 27
The line 284 between the flowmeter 8 and the in-line mixer 272 includes a flow indicator 288 and a check valve 290.

In a commercially feasible embodiment, pump 254 and in-line mixer 272
And the line 28 between the pump 278 and the in-line mixer 272
Reference numerals 4 each include a pressure relief valve (not shown). The silicate solution and the aluminum sulfate solution may block in the pipeline, and the pump 254 and the pump 27
8 will continue to pump at the same rate even if such an occlusion occurs. Thus, this occlusion can cause a significant pressure increase within the device 200 in a short period of time. By providing pressure relief valves at strategic locations, such pressures can be relieved as needed. The silicate mixture and the aluminum sulphate source are mixed together by the in-line mixer 272 and thereby reacted to produce a homogeneous mixture. Alternatively, in embodiments where aluminum sulfate is not added to the FLOCC, the in-line mixer 272 can be omitted. In the working example, the in-line mixer 272 is a static pressure in-line mixer model no. 3 / 4-40-
3-12-2. In a commercially available embodiment, the in-line mixer 2
Reference numeral 72 may be a Comax static pressure mixer.

The FLOCC exits the in-line mixer 272 and is fed through a line into a carbonator 300 (see FIG. 12, carbonator 106). In a commercially available embodiment, a line 302 between the in-line mixer 272 and the carbonator 300 is provided with a pressure indicator 304 (indicated by PI in the present drawing). The carbonation device 300 comprises at least one carbonation unit 306 (the device 200 of FIG. 13 comprises only one carbonation unit. See FIG. 14 for further details of the carbonation unit). ), Each carbonation unit preferably comprises a carbonation line 310, which connects a series of diffusers 312 that diffuse carbon dioxide into the silicate mixture. Preferably, the carbonation line 310 includes a series of bends to agitate the FLOCC to assist in the diffusion of carbon dioxide into the silicate mixture. A multiple pH indicator 314 (denoted as PH throughout the drawing) is located in the carbonator 300 to monitor the pH of the silicate mixture.

FIG. 14 shows an example of the operation of the carbonation unit 306 with a series of diffusers 312. In the working example shown in FIG. 14, the carbonation unit 306 has eight diffusers. In the illustrated embodiment, each "T" shaped pipe fitting is:
Adapted to accommodate diffusers. This “T” shaped pipe fitting is fluidly connected and forms a carbonation line 310. Inside each diffuser 312, after the silicate mixture enters through the first opening 316, the flow direction changes 90 degrees and exits through the second opening 318. This change in direction stirs the silicate mixture and aids in diffusion and mixing. Carbon dioxide gas is supplied through the third opening 320. If carbon dioxide is not sufficiently diffused into the silicate mixture with a series of eight diffusers, then more diffusers can be added to carbonation unit 306, or other diffusers can be added. A carbonation unit can be added to the carbonation device 300 in series with the existing carbonation unit 306. An in-line mixer, such as in-line mixer 272, can be added between the carbonation units to agitate the silicate mixture.

Referring now to FIG. 15, a working example carbon dioxide diffuser 312 is shown in greater detail. The carbon dioxide conduit 330 extends through the first threaded nut 332 and extends through the small diameter first end 336 into the cylindrical bulkhead fitting 334. The first end 336 of the bulkhead attachment 334 preferably has an outwardly extending thread adapted to engage the first nut 332. The first nut 332 is preferably slip fitted over the first end 336 of the bulkhead fitting 334 and presses the gasket 338, thereby causing the gasket 338 to move onto the carbon dioxide line 330. Pressure is applied inward to form a sealed portion. Returning toward the “T” shaped pipe fitting, the first end 336 of the bulkhead fitting 334 is connected to the radial wall 3 of the threaded plug 344.
It extends through an axially extending opening 340 formed in. The threaded plug 344 includes an outwardly extending thread that is adapted to inwardly extend the thread formed on the wall surrounding the "T" shaped pipe fitting opening 320 (see FIG. 6). Engage. A second end 346 of the bulkhead fitting 334 forms an outwardly extending head or forms a flange disposed within a threaded plug. Annular gasket 348, which is preferably made of rubber, is located between second end 346 of bulkhead fitting 334 and radial wall 342 of plug 344.

Returning to the opposite side of the radial wall 342, the second nut 350
Engage a thread that extends outwardly of the first smaller diameter end 336 of the bulkhead fitting 334. The second nut 350 is the radial wall 3 of the threaded plug 344.
42, whereby the second nut and the second end 346 of the bulkhead fitting 334 are tightened onto the radial wall of the threaded plug. Annular gasket 348 is attached to bulkhead fitting 334.
Between the radial wall 342 and the second end 346 to form a sealed portion. Returning further to the "T" shaped pipe fitting, the second end 346 of the bulkhead fitting 334 forms an inwardly extending screw (not shown). Filter 360
Has a first end 362, the outwardly extending screw engaging an inwardly extending screw formed in the second end 346 of the bulkhead mount 334. The porous second end 364 of the filter 360 further extends into a “T” shaped fitting. In a preferred embodiment, the second end 3 of the filter 360 is
The diameter of the opening in 64 is between 60 and 110 microns. The porous filter 360 may be a “Capstan Permaflow No. FAP 100 F30” brass porous filter.

In operation, CO ₂ is supplied from the CO ₂ gas line 330 to the bulkhead fitting 33.
4 and into the filter 360. The filter 360 separates the CO ₂ into fine wrinkles, which diffuse more easily into the silicate mixture. Diffusion into the silicate mixtures CO _2, it can be achieved by other devices for diffusing pressurized gas into the conduit in carrying the liquid should be understood. Returning to FIG. 13, the CO ₂ source (see CO ₂ source 108 in FIG. 12) is preferably a pressurized gas container 366 or a dewar for gas removal or distribution. The variable valve 368 is arranged at an outlet of the gas container 366. The gas is supplied into a plurality of gas lines 372 arranged in parallel by a gas line 370 extending from the gas container 366. Each of these side-by-side gas lines 372 includes a variable valve 374, a flow meter 378, and a non-return valve 380 controlled by a solenoid 376 (denoted as S throughout the drawing). The side-by-side gas lines 372 may branch into further parallel gas lines, each of which supplies CO ₂ to the diffuser 312.

As the silicate mixture travels through the carbonator 300, the diffusion of CO ₂ into the silicate mixture allows for the production of carbonic acid in the silicate mixture. This carbonic acid then reacts with the silicate, lowering the pH of the silicate mixture and accelerating the polymerization process. As the pH decreases, the aluminum sulphate initially formed by the polymerization reaction of the silicate mixture crosslinks, causing the silica particles to gel. However, when the silicate mixture leaves the carbonator 300, a cure time is still required to cause an optimal amount of crosslinking reaction before feeding into the paper machine. The curing device 400 (see curing device 110 in FIG. 12) allows time for the FLOCC to fully crosslink, but preferably the FLOCC in the curing device.
To ensure that it does not over-solidify. The main curing device 400 preferably includes a curing conduit 402, a reaction tank 404, and a run tank 406. Preferably, the curing device 400 begins with a curing conduit 402 extending from the carbonation device 300. Moving the silicate mixture or reaction mixture through the cure conduit 402 causes a polymerization reaction process. In a commercially feasible embodiment, the pressure indicator 412 and the pH indicator 414 are also
Place in 2. Pressure indicator 412 couples to a pressure relief valve (not shown).
The pH indicator 414 preferably signals a pH indicator controller (PHIC) 416 that indicates the pH of the silicate mixture. The current 416 from this pH indicator is sent to control the solenoid 376, and the solenoid 376
Control the valve 374 for the middle CO ₂ line 372. Thus, the amount of CO ₂ varies depending on the pH of the silicate mixture. In this way, the device 200
A silicate mixture having the desired pH can be produced.

Preferably, the silicate mixture is fed into a reaction tank 404 by a curing line 402. The silicate mixture is stirred in the reaction tank 404 by the stirrer 420. The dewatering line 422 extends from the bottom of the reaction tank 404 and
Is provided with a shut-off valve 422 that is normally closed during the operation. The silicate mixture is supplied from reaction tank 404 to line 426 located near the top of the tank.
After flowing through the inside, the tank is emptied and enters the run tank 406. The reaction tank 404 may include a plurality of outlet lines (not shown) that flow at different liquid levels. Each outlet line is preferably provided with a shut-off valve. During use, one of the outlet lines is opened and the level of the silicate mixture in the reaction tank 404 rises to the level of the open outlet line. Therefore, the liquid level in the reaction tank 404 is
It is changed by opening different outlet lines. By changing the tank level, the time during which the silicate mixture remains in the reaction tank 404 changes when the flow rate into the apparatus is kept constant. In this way, the device 200
An optimal time for the silicate mixture to gel can be obtained. By providing another reaction tank and arranging it in series, the polymerization reaction time of the silicate mixture can be further secured. Such an embodiment is suitable for portable, commercially available devices.

Preferably, the FLOCC product in run tank 406 is agitated by stirrer 428. Stirrer 428 may be of the same type as stirrer 234 described above. In a commercially feasible embodiment, run tank 406 includes a level transducer 430 that sends a signal to a level indicating controller (labeled LIC) 432. FLOCC flows out of the run tank 406 into a carbonation treatment 440 located near the bottom of the tank. In a commercially feasible embodiment, then the pump 44
2 pumps the FLOCC through line 444, which preferably draws the suction side of the paper machine fan pump 446 (see fan pump 112 in FIG. 12: see pump 30 in FIG. 13). Line 444 further includes a magnetic flow meter (
448) and a flow transmitter 450, which sends a signal to a flow indication controller 452 indicating the flow rate through the line. Pump 4
42 is preferably driven by a motor 454, which is controlled by a flow control 452. Pump 442 is preferably of the same type as pumps 202, 204, 278 described above, but is preferably a 7.5 horsepower motor.

A line 444 between the pump 442 and the fan pump 446 is preferably connected to a diversion line 460. The water diversion line 460 is provided with shutoff valves 462, 464, which are normally closed, but when they open, the FLOCC flowing out of the pump 442 is connected to the valve (the valve 462 and the valve 462). Either dewater from the device 200 (by opening both of the 464) or divert back to the run tank 406 (by opening the valve 462 and closing the valve 464). . Preferably, the flow in the apparatus 200 ensures sufficient time for a suitable polymerization reaction to be obtained, to obtain a suitable composition of FLOCC, and to produce an appropriate amount of FLOCC for the papermaking process. The device 200 is controlled as described above. Starting from the water line 238, the flow control device 246 causes the liquid level instruction control device 23
From 2, a control signal indicating the level of the silicate mixture in the premix tank 218 is received. If the liquid level is too low, the flow of water to the premix tank 224 is increased by the flow rate instruction controller 246. If the level is too high, the flow of water into the premix tank 224 is reduced by the flow control 246. The flow indication controller 246 for water sends a control signal 512 to the liquid flow indication controller 210, which regulates the flow rate from the pump 214 into the premixer 224, and thereby the premixer and the premixer in the water line 238. The flow into line 220 is substantially constant. The liquid flow rate instruction control 210 sends a signal to the liquid flow rate instruction control 212 to regulate the flow rate through line 222 so that this flow rate remains proportional to the flow rate through line 220. I do. Accordingly, the composition of the silicate mixture flowing into the premix tank 218 is maintained substantially constant, and the level of the silicate mixture in the premix tank is maintained substantially constant.

The liquid level indicating controller 432 indicating the level of the FLOCC in the run tank 406 sends a signal to the flow rate indicating controller 262, which controls the pump 254. If the level is too low, the speed of the motor 260 is increased to increase the flow of the silicate solution in the device by the flow indicator controller 262. If the level is too high, the speed of the motor 260 is reduced to reduce the flow of the silicate solution in the device by the flow control 262. This flow rate instruction control device 262
Thus, a signal indicating the flow rate passing through the pump 254 is sent to the flow rate instruction controller 282 that controls the pump 278. Next, the flow command controller 282 changes the speed of the motor 280 to regulate the flow rate through the pump 278 and
And line 284 to maintain the proportion of each flow. Thus, the composition of the silicate mixture entering the carbonator 310 and the level in the run tank 406 are substantially constant.

The pH instruction control device 406 is a flow rate instruction control device 2 that controls the solenoid 376.
A signal is sent to 82 to control the flow of CO ₂ into diffuser 312 by the solenoid. This solenoid regulates the flow of CO ₂ into the diffuser, thereby altering the carbonation rate of the device and thereby the p of the resulting silicate mixture.
Change H. Making these adjustments ensures that the silicate mixture is formed at a substantially constant pH indicator and that an appropriate amount of polymerization occurs in the apparatus 300. The paper machine outputs a signal 530 indicating the machine production speed of the paper to the flow rate control device 4.
The flow control controller 452 adjusts the speed of the motor 454 so that the flow rate of the FLOCC passing through the line 444 and entering the paper machine is adjusted.

In a commercially feasible embodiment, the overall control of the various motors and valves within device 200 is controlled by a computer that processes signals from the user or a computer that processes signals from transducers and indicators. Run by. The computer then sends control signals to the valves and motors, as described above. In a commercial embodiment, a PC (personal computer) can be used. In a specific working example of the present invention, one or two carbonation units 306 with eight diffusers 312 are provided. The curing conduit 402 of the present embodiment is separated into a plurality of conduit segments, and an in-line mixer (not shown) is provided between each segment. The stiffening conduit 402 includes a first segment having a length of 50 feet, a second segment having a length of 45 feet, and a third segment having a length of 50 feet. Within this embodiment, the length of the conduit extending between the pump 442 and the fan pump is 50 feet. The following table shows some preferred examples of FLOCC retention times within each segment of the device 200,
To the in-line mixer 272 and ends with the introduction of FLOCC into the paper machine headbox 446. These times allow the silicate mixture to be fully polymerized in the apparatus 200, and before reaching the reaction tank 404,
Ensure that the LOCC does not cause premature crosslinking or gelling between the lines. Also, these times are sufficient to produce paper at the FLOCC indicated percentage ratio in the paper machine of 160 pounds per hour.

[0066] Apparatus described above, thoroughly mixed FLOCC, the CO ₂ is diffused into the silicate mixture, as long as to allow crosslinking of time sufficient without causing excessive solidified conduit is It should be understood that can be changed in many ways. For example, in the present apparatus, instead of using the reaction tank 404 and the run tank 406, sufficient crosslinking can be performed by providing an elongated curing conduit.

C. Chemical Laws for Generating Inorganic Network In producing a product having a cellulose-inorganic network, an inorganic network including fibrous material is generated. One method for combining fillers to form an inorganic network employs alkali and / or alkaline earth metal silicates. Without being bound by a single law of operation, it appears that silicate polymerization is the mechanism that explains the formation of the present inorganic network. Polymerization of silicates occurs by a condensation reaction between two silanol end groups (or silicate groups), which results in water and a silicon-oxygen-silicon bond (Si-O-Si) (reaction 1). reference).

(Equation 1)

Reaction 1 As the silicate polymerization reaction proceeds, the silicate components are covalently bonded to each other and the fibers are trapped in the silicate polymer thus obtained. Silicon is the second most abundant element in the earth's crust. Silicon is not found in its elemental form in nature and occurs primarily as oxides and silicates in combination with oxygen, the most abundant element. Silicon and oxygen, combined with other elements, make up most of the minerals on earth. Therefore, many of the papermaking fillers include silicon dioxide (precipitated silica, diatomaceous earth, etc.) and silicates (kaolin, clay, talc,
That is not surprising. These minerals are commonly referred to as shared network solids, which are crystal lattices of atoms, all of which are connected by a three-dimensional infinitely extending network of polar or non-polar covalent bonds. I have. Commonly used paper fillers, such as clay, talc, silica, etc., do not exhibit the binding behavior as in Reaction 1 during the production of paper products made by processes developed prior to the present invention. This is because silicon is already polymerized or condensed to form a solid having a covalent network structure. Thus, such materials will not subsequently polymerize in the presence of the fibrous network to create an inorganic network around the fibrous web. In essence, we are dealing with the depolymerized components, and then proceed with the polymerization reaction around, over, and around the material.

The silanol condensation reaction process can be extended to include other elements. For example, one of the silicon atoms in the condensation reaction can be replaced by aluminum. In this way, a shared network solid can be formed, in which some silicon atoms have been replaced by aluminum atoms in a three-dimensional framework of SiO ₄ tetrahedrons, in which any oxygen is replaced by two. Is shared between the four tetrahedra. Whenever aluminum replaces silicon in this three-dimensional framework, the framework concept is negatively charged and other cations must be uniformly distributed in the framework. These aluminosilicates are the most widely distributed, extensive and useful silicate minerals in nature. Thus, materials such as aluminum sulphate, sodium aluminate, sodium stannate, sodium orthoborate decahydrate, metal phosphate, etc., are elements that can replace silicon during the condensation process (aluminum, tin, boron). , Phosphorus, etc.), it can be used to produce a shared network solid also when producing the composite product.

In silica, silicates and aluminosilicates, silicon is always tetrahedral bonded to four oxygen atoms, but its covalent bonds exhibit significant ionicity. The SiO ₄ tetrahedron is the basic structural unit in these materials, occurring alone or sharing oxygen atoms, occurring as a small group, occurring as a small cyclic group, occurring as an infinite chain, It occurs as a planar sheet or as a three-dimensional framework. Oxygen, or silicon dioxide (commonly known as silica), naturally occurs in various forms (sand, quartz, flint, etc.), and consists of a network structure in which silicon and oxygen are continuously bonded. Is bonded to four oxygens, each of which is bonded to two silicons. If the metal carbonate fuses with the silica at elevated temperatures, carbon dioxide is evolved, resulting in a complex mixture of metal silicates. In essence, the covalent network solid is depolymerized by cleaving the silicon-oxygen-silicon bond. If an alkali metal carbonate is used in this fusion and the mixture is rich in alkali, the product is water soluble. However, when the alkali content is low, the metal carbonate is still insoluble (not fully depolymerized). Theoretically, the high alkali content, must be able to generate separate SiO ₄ ^{4-(orthosilicate)} anion, the alkali silicate solution is usually complicated polymerizable anion A good mixture. The only silicate that is water soluble is the alkali metal silicate. Alkaline earth metal silicates are not soluble in water.

The fusion of metal carbonates with silica, silicates and aluminosilicates has been utilized in many industrial processes, from the production of cement to the production of sodium silicate. The covalent network solid is depolymerized by cleaving the covalent bond (silicate-oxygen-silicon bond) and the product is a metal salt of polysilicic acid (hydrous silicon dioxide). When the alkali or alkali metal content of the fusion product (metal silicate) is high (depolymerization is high), they are basic. If these products are added to water or neutralized, silicic acid or polysilicic acid (silanol end groups) is generated, which is polymerized according to the reaction formula 1 to regenerate a covalent network solid. According to the method of the present invention, using this process,
Cellulose fibers can be entrapped in the mineral network to create new composite materials. Another possible solution for producing the composite product of the present invention is to utilize the usual abbreviations employed by cement chemists. C3S = 3CaO. SiO ₂ C2S = 2CaO. SiO ₂ CS = CaO. SiO ₂ C = CaO CH = Ca (OH) ₂ C—S—H = Calcium silicate hydrate gel with variable stoichiometry S = SiO ₂ H = H ₂ O Calcium silicic acid to water Addition of the salts (C3S, C2S, CS) gives a calcium silicate hydrate gel and calcium hydroxide (see reaction 2).

Reaction 2 In the presence of C3S, C2S, and / or CS + H → CSH + CH pozzolan, the calcium hydroxide further reacts to form additional calcium silicate hydrate gels (reaction (See No. 3: called the pozzolanic reaction).

Reaction 3 Pozzolan or S + CH + H → CSH

Pozzolans are defined as siliceous or siliceous and aluminous materials that have little or no cement value of their own, but are in a finely divided form, and are hydroxylated in the presence of moisture. It chemically reacts with calcium at room temperature to produce a compound having cement properties. Examples of natural pozzolans are diatomaceous earth, opal chert and some shale. Igneous materials such as pumice and tuff are generally less active, while materials such as clay require calcination or heat treatment to make them reactive. Although ground blast furnace slag has some cement properties, it can be considered to be pozzolan. Calcium silicate hydrate gels undergo silicate polymerization that binds the filler particles (calcium silicate, silica, etc.) together. Utilizing the reaction of these calcium silicates (C3S, C2S and / or CS), the method of the present invention is practiced to produce a covalently linked inorganic network solid and entrap fibers in the inorganic matrix. You can also.

D. Ratio of Percentage Increase in Break Length to Percentage Ash Content One major object of the present invention is to increase the ash content while increasing the strength of the paper. One such indicator is the ratio of the percentage increase in tear length (fracture length) to the percentage ash content. This increase in break length is a percentage of the increase in break length when compared to a control sample without silicate. The ash percentage ratio is the percentage of material remaining after burning the sample at 500 ° C. The percentage ratio of silicate applied is based on oven-dried handsheet stock (fiber, filler,
Weight percent of oven-dried sodium silicate added to sodium silicate, etc.). This percentage increases as the ash content increases. This is because the mineral network accounts for a larger percentage of the total mass. Therefore, as for the inorganic component imparting strength to the composite, the percentage should increase as the percentage ratio (ash percentage ratio) of the total composite increases. As the ash percentage ratio increases, the ratio to normal filler remains relatively unchanged. Because it does not contribute to the strength. Also, as the concentration of silicate increases, this proportion must increase. This is because it is a component that imparts strength to the composite, as opposed to other fillers.

The specific percentage of ash content is from about 5% to about 30%, and silicate concentrations of 3.4% and 12.1% are shown in Table 18.

III. Pre-agglomeration of Filler Using Starch Granules A method for producing paper by pre-agglomeration of filler particles using starch granules includes the following steps, some of which include: It can be optional to make a manufacturing embodiment: the step of providing a starch, which can be processed to form an adhesive granule with suitable dimensional characteristics; Processing to form expanded starch granules; filler particles-forming a fine floc of starch by mixing the filler particles with the expanded starch granules; and the particles -Combining the fine floc of starch with the cellulose furnish to form a paper product. Each of these steps, and the materials used to perform each step, are described below.

A. Materials 1. Starch Two features were first considered for the selection of starch for practicing the present invention. First, the appropriate starch can be processed to form starch granules. Second, these formed starch granules preferably have a granule size within the desired granule size distribution. One advantage of the present invention is that the method comprises repeatedly treating the starch to form granules having an optimal and preselected granule size and size distribution, and to produce a paper product having the desired characteristics. That is.

For example, copy (ie, xerographic) paper can be made by this method. An example of the manufacture of these products is by using starch granules having a granule size in the range of about 15 μm to about 150 μm, preferably about 40 to about 70 μm, and even more preferably about 50 to about 60 μm. It was conducted. The standard deviation of the fine grain size is about 20 μm. In the example of the production of paper products made with steamed pea starch, pea starch, which when processed produces fines having an average size of about 56 μm, was typically used.

One primary purpose of using starch granules is to agglomerate the filler particles and to bind such filler particles to the starch granules. Therefore, it is possible to compare the aggregating ability of the starch granules and the peptization resistance. While the present invention is not limited to one theory of action, it is believed that at present there is a charging phenomenon associated with the starch's ability to agglomerate this filler particle. It is believed that the protein associated with a given starch increases the starch's ability to aggregate filler particles,
This has not been fully verified. As a result, these starches have charge properties that sufficiently agglomerate the filler particles, possibly via related proteins, and these starches also appear to be candidates for practicing the present invention.

The size and size distribution of the starch granules and the ability to agglomerate the filler particles
It depends on the type of plant from which this starch is derived. For these paper products listed above, the following various starches have proven useful in making starch granules having the appropriate dimensional characteristics included:

Plants belonging to the legume family, such as peas and kidney beans, are particularly suitable sources of starch for practicing the present invention. Pea starch is currently a preferred material because it satisfies the two criteria described above and further proved to be an excellent flocculant for filler materials. .
Preferred pea starches are under the STARLITE mark in Canada,
Commercially available from Parrheim, Saskatchewan. STARLIT
E pea starch has been dry ground and air classified to remove undesired materials. Wet treated pea starches have also been tried, but did little to work like dry treated starches. STARLITE's pea starch is derived from pea and is unmodified and air classified to provide large starch particles. STARLI as sold
The size of the particles of TE is about 23 μm. STARLITE is a white, commercially available free-flowing powder with a water content of about 10% to about 13%, about 6.5%.
PH for cooked starch, and amylose content of about 35%. S
Chemical analysis of TARITE shows that it has about 84% starch, about 5% protein, about 4% sugar, about 1% lipid and about 1% ash.

The potato starch (bud and whole potato) was also tested. These starches produce sufficiently large granules than pea starch, for example, about 265 μm in potatoes compared to about 60 μm for pea starch. Potato starch may have more related proteins than corn starch and may therefore be an even more preferred flocculant. Potato starch is also amphoteric, which is advantageous because starch can form the desired result for cations or anions, depending on the pH of the system, and for certain paper compositions. However, potato starch also forms granules with an average particle size slightly larger than pea starch, which is one reason that pea starch is currently the preferred starch material.

[0084] Pearl corn starch was also tested and proved to be useful for producing products according to the method of the present invention. Modified corn starch was also tested, but the modified corn starch tested tended to dissolve during the water treatment instead of forming granules. Modified starches or groups of starches are known or have been manufactured and, as long as they form fine granules with suitable dimensional characteristics by processing according to the claimed method of the invention. Occasionally, such a material is or may be a sufficiently suitable source of starch.

Based on the above, starches currently believed to be most useful in practicing the present invention are plants belonging to the legume family, particularly pea starch, potato starch, corn starch, and It is selected from the group consisting of starch from their mixtures.

One main purpose of using the starch granules is to agglomerate the filler particles and to bind such filler particles to these starch granules. Therefore, it is possible to compare the aggregating ability and peptization resistance of these starch fine granules. Although the present invention is not limited to one theory of action, it is believed that there is presently a surface charging phenomenon associated with the starch's ability to agglomerate this filler particle. Proteins associated with a given starch may increase the starch's ability to aggregate filler particles, but this has not been fully established.

[0087] 2. Filler Particles In general, the method of the present invention can be practiced with any filler material useful for making paper products. This filler material can be agglomerated using starch granules made as described herein. A partial list of such filler materials includes, but is not limited to, calcium carbonate, precipitated calcium carbonate (PCC), ground calcium carbonate, chalk, clay, titanium dioxide, talc, dolomite, Includes calcium sulphate, barium sulphate, dolomite, aluminum hydroxide, salt white, and mixtures thereof.

[0088] 3. Additional Paper Additives In addition to fillers, materials commonly used to make paper products can also be used in combination for pre-agglomeration of filler particles with a particular starch.
For example, paper additives such as sizing agents, cationic starches, dyes, wet and / or dry strength agents, and mixtures thereof can be used. An embodiment of the production of the present invention is the use of starch granules, for example steamed pea starch granules,
It was mixed with a cationic polymer, such as polyaluminum chloride, to promote pre-agglomeration of the filler particles.

In addition, retention chemicals and discharge aids commonly used in the wet end of paper manufacture can be used in combination with the filler particles agglomerated using starch granules. Without limitation, such materials which may be useful for use in conjunction with the filler-particle / starch fine flocculent of the present invention include cationic starch, cationic polyacrylamide, cationic Polyamide, polyimide, polyamine, polyaluminum chloride, alum, chlorohydroaluminum, cationic metal ions, for example, calcium ion, magnesium ion,
And ferric ions, and mixtures of these substances.

B. Processing of Starch to Form Starch Granules The appropriate starch, selected as described above, is then processed to form starch granules having the desired average granule size and distribution, and filler particle agglomeration characteristics. I do. These processing steps include the steps of processing starch to form starch granules, aggregating filler particles with starch granules, and adding starch to the cellulose furnish to produce the desired paper product. -Adding a fine flocculent precipitate of fines / filler particles. The method can also optionally include the step or steps of adding an additional material, such as a starch cationizing agent, to either the starch, the filler particles, or the fine floc.

1. Formation of Starch Granules Initially, the desired amount of starch is obtained. The amount of starch depends on the amount of filler added, as well as on the starch-to-filler ratio used. Embodiments of the manufacture of paper products include, in accordance with the method of the present invention, a ratio of filler particles: starch granules of at least about 1: 1 to about 25: 1, and even more typically at least 10: 1.
, Preferably from about 15: 1 to 22: 1, and even more preferably about 18: 1. If there is too little filler or too much filler,
It may not be of the correct strength and may be detrimental to paper properties. For example, if too much filler is used, then the ratio of starch to filler particles used will be too high, and the cost of producing paper products will increase significantly. If too little starch is used, then insufficient starch will agglomerate all the added materials. Fine flocculents, free of fillers and pigment particles, are not well retained during the papermaking process and also form dust after the production of the product.

[0092] Once the desired filler particle: starch granule ratio is determined, an aqueous starch dispersion is then formed using the appropriate amount of starch. This dispersion is
Typically, it includes a dispersion of starch in cold water. The relative amounts of starch and water are governed and can be varied depending on the treatment to be taken into account, for example with stirring. If too much solids are used, then it is difficult to mix / stir the dispersion. This practical upper limit is probably about 10% solids by weight. The actual minimum is the amount by which a product having the desired characteristics is formed. At present, the amount of starch to be used is from about 0.1% to about 10% by weight, preferably about 1%
From the above it appears that it should be about 6% by weight, which is typically consistent.

Next, the aqueous dispersion is heated while stirring. The purpose of heating the starch is to change the physical form of the starch from that of the crystalline form of the starch to discrete swollen granules. FIG. 43 illustrates the effect that heat treatment has on starch. In general, starch is a high molecular weight substance and is poorly soluble in water. These starches can be dispersed in water and, when heated, begin to swell and further increase the viscosity of the dispersion. If heated too long at too high a temperature, these starch particles will eventually burst. The starch must be processed with ordinary knowledge and the starch dissolved in water. These dissolved starches are added to the filler particles to form a film on the filler particles and bind the particles. One feature of the present invention is that a flocculent precipitate of filler particles is produced more efficiently and that the starch is processed up to the fine-grain stage rather than forming a starch solution, and then these It is recognized that the agglomeration of filler particles using starch granules produces a more efficient, even more preferred, and more reproducible size distribution.

The temperature at which the aqueous dispersion is heated to form the starch granules can vary, but generally will be at least about 50 ° C. to about 120 ° C., and more preferably about 70 ° C.
C to about 90C. Starch is cooked in a pressure vessel and starch granules are produced by the method of the present invention, but as the temperature increases, these granules begin to degrade or burst. Aqueous dispersions of starch are cooked at the boiling point of water, or even higher, but this is not the case. Rather, aqueous dispersions of starch are typically
Steam from about 85 ° C to about 90 ° C for about 5 minutes.

[0095] Steaming starch using pressure steam is common in paper mills and this process is referred to as "jet steaming". The temperature and pressure of the pressure steam are substantially higher than those at atmospheric pressure. The "jet" not only steams the starch, but also ruptures the starch particles. Although the particles can be agglomerated using the jet-cooked starch particles, the size and distribution of the agglomerated material produced by the jet-cooking can be at temperatures from about 85 ° C. to about 90 ° C. and at about 1 atm. Do not match those produced by steaming.

After this first heating step, the heated dispersion is then diluted and at a temperature below the processing temperature, but typically at about 50 ° C., even more typically It is cooled to about 70 ° C. The dispersion is then kept at this temperature with stirring until used in the next step operation. This is achieved by dilution of the aqueous dispersion of starch with hot water to a concentration of about 2% to 3%.

The heating operation described above is a typical heating treatment used to treat pea starch. However, the heat treatment is best determined by the nature of the fines produced by this process. FIGS. 40 and 41 show micrographs of the starch before the above-described treatment and the heat-treated starch, respectively. These micrographs show the deformation that occurs when starch is heat treated in this way,
And furthermore that the desired feature is swollen starch granules of sufficiently uniform size,
It is clearly shown.

[0098] 2. Optional starch cationization step The cationizing agent can then optionally be mixed with the starch. The purpose of the addition of the cationizing agent is to enhance the flocculating capacity of the starch. Suitable cationizing agents include
It includes polyaluminum chloride (PAC), chlorohydroaluminum, alum, cationic retention aids, acids, salts and mixtures thereof, and PAC is currently the preferred material.

[0099] The amount of cationizing agent used depends on the nature of the drug selected. For PACs, the current upper limit appears to be PAC and starch in a 1: 1 weight ratio, and the lower limit appears to be about 1% by weight PAC based on the weight of the starch. Currently, the preferred amount of cationizing agent is based on the amount of starch added,
From about 10% to about 20% by weight.

Starch: The cationizing agent can be added to the dispersion in various ways. Good results have been obtained by adding PAC with water used to dilute the cooked starch.

3. Agglomeration of the filler particlesThe filler is then added to the dispersion of the cationized starch with vigorous stirring, or they are pumped into small containers and mixed or pumped together, And in a static mixer. Generally, the filler is warmed, for example, to a temperature of about 45 ° C to 60 ° C. The reason is simply that it is conveniently used after manufacture. However, heated fillers can also facilitate the agglomeration process. In addition, cold fillers will lower the temperature of the aqueous dispersion of the cationized starch. As the temperature of the dispersion drops below about 50 ° C., the aqueous dispersion begins to gel rapidly.

[0102] 4. Addition of the agglomerated filler to the cellulose furnish Once agglomerated as described above, the filler then seeks to associate with the cellulose furnish. This agglomerated filler is up to the fiber system preceding the headbox, such as a discharge pump or a mechanical pump. This pre-agglomerated material is correctly added to the pump. The reason for this is that it provides good mixing of the cellulose with the furnish.

[0103] 5. Addition of Filler Particles and Steamed Starch to Cellulose Furnish Steamed pea starch can be added to a cellulose furnish containing a filler dispersion and retained by a retention aid. . These filler particles agglomerate and are retained as in normal wet end processing, and do not selectively agglomerate on starch granules. By doing so, the strength of the paper can be improved.

6. Retention Systems All retention systems commonly used at the wet end of paper manufacturing processes can be used in combination with the starch agglomeration process of the present invention. Without limitation, a partial list of such retention aids includes cationic polymers, anionic polymers, alum, polyaluminum chloride, chlorohydroaluminum, cationic particles, anionic particles, cationic or anionic. Included are microparticles, and mixtures thereof, especially combinations of anionic and cationic materials.

D. Experimental Machine Results Paper products were produced on a test scale paper machine using the method of the present invention. Predetermined results from these attempts are shown in FIGS.

FIG. 46 shows how the tear length of the experimental machine varies between control paper and paper produced with increasing ash content according to the method of the present invention. The breaking length for paper made according to the present invention was comparable to that made by pre-agglomerating the filler particles with the starch granules. There was little or no improvement in strength for paper made with the pre-agglomerated filler, probably for two reasons. First, the amount of cationic wet-end starch added (about 7.26 kg / ton) added to the control run significantly increased the strength of the paper, and using pre-agglomerated PCC of pea starch. Over or equal to the improvement in strength of those manufactured. Second, there is a significant size increase, as shown in FIG. The use of pre-agglomerated PCC ironically reduces fiber fonding and reduces paper strength.

FIG. 47 shows how the size changes with increasing ash content between the experimental control paper and the experimental paper manufactured according to the method of the present invention. Size is a measure of the tendency of paper to absorb water or absorb water, and measures the time required for absorbed water to be in seconds. FIG. 47 shows that the paper produced on the experimental machine has a significantly better size compared to the control. At an ash content of 20%, the control has a size of about 100 seconds, whereas a paper made according to the process of the invention has a size of about 300 seconds at a ash content of 20%. Furthermore, increasing the ash content of the paper produced according to the invention to 30% reduced its size to 100 seconds. Pre-agglomeration of the filler reduces the absorption of the size chemicals into the filler particles and leaves the size chemicals to be absorbed on the filler surface, thus improving the size efficiency.

FIG. 48 shows how the strength of the paper changes with increasing ash content for the experimental control paper and the experimental paper manufactured according to the method of the present invention. FIG. 48 clearly shows that the method of the present invention substantially increases the strength of paper produced without starch and without pre-agglomeration of the filler particles. Further, with respect to the pea starch used without pre-agglomeration of the PCC slurry and the filler particles, FIG. 48 shows the strength of paper produced with and without pre-agglomeration of PCC. All three groups of papers were made using about 4.54 kg / ton of starch (cantonic starch), with the addition of non-starch in the control run, but in the run shown as PCC slurry and pea starch.
Various amounts of pea starch were added, equal to the amount of pea starch used to pre-aggregate the PCC and added to the wet end. For example, 15%
When pre-agglomerated PCC is added, the pea starch used to agglomerate the PCC is equal to about 7.71 kg / ton of total furnish, and about 7.71 kg / ton.
kg / ton of pea starch was added to the furnish along with a 15% PCC slurry. In the operation of the pre-agglomerated PCC, no additional pea starch was added and about 4.54 kg / ton of cationic wet end starch was added.

FIG. 49 shows how opacity changes with increasing ash content for experimental control paper and experimental paper manufactured according to the method of the present invention. FIG. 49 shows that the opacity of the experimental paper made in accordance with the present invention is generally higher than that of the control paper, and furthermore, it affects the range exhibited by the control paper by increasing the ash content. Indicates no. At an ash content of 30%, the paper made according to the method of the present invention had an opacity of 92% or more, while for the control paper the opacity was 91% or less.

IV Examples The following examples are provided to illustrate some features of the present invention. These examples should not be construed as limiting the invention to the particularly recited features.

Example 1 This example describes one embodiment of the present method for forming a paper product, wherein the inorganic material (mineral (mineral)) around the fibrous fraction of the composite product is described. Prove to produce a mesh structure. The handsheets produced according to this example and their components are
Summarized below 1.

About 30 g (oven-dry basis) of a fibrous slurry [80% scoured poplar (hardwood) and 20% scoured pine pine (softwood)] measured at 2.46% strength in a 2000 ml plastic container did. As described in Table 1, precipitated calcium carbonate (HB PCC from St. Helens Mill) and / or calcium oxide (CaO Technical powder MCB CX267 CB1175)
The fibrous slurry was agitated while adding the amount of). Calcium oxide was added only to T6 and T9. If completely reacted with carbonic acid, add enough calcium oxide to PCC22.
3%. After stirring for 5 minutes, sodium silicate N solution (National Silicate Ltd. Toron)
to, Ont. 51.37% oven dried base) was added to all test samples (not to control). Except for adding an additional amount of sodium silicate to T5,
The ratio to CC was kept constant. 1.4% by weight of calcium oxide was also added to T9.

The sample was carbonated by feeding carbon dioxide to the mixture using a carbon dioxide gas cylinder fitted with a gas diffusion tube. Approximately 1.
Continuing for 5 hours, the pH value of the mixture was reduced from about 7 to 8. The carbon dioxide transfer pressure was very low (about 1 psi) and the starting pH was relatively high, about 10-11 (EM Sience color pHa).
st specimen). Test sample T6 with calcium carbonate without PCC was carbonated for more than about 1 hour, thereby bringing the same pH value to about 7 to 8. The stock was diluted to 4 liters and stirred while 2% starch or alum was added. The cationic starch was Hi-Cat168 cationic potato starch from Roquette Corp. Thereafter, 0.035% Percol 175 (a retention aid) was added with stirring. The starch step was omitted for the first control C1.

After all the substances were added and the carbonation step was completed, stirring was stopped and a handsheet was made. All handsheets were formed on Noble & Wood square handsheet molds, wet felt pressed at 20 psi, and dried on a drum dryer at 200 ° F. The target base weight of the handsheet made according to this example was 60 g / m ² . Handsheets were prepared according to TAPPI T222 and tested in the same environment. Tensile tests were performed on 7.1 inch specimens at a crosshead speed of 1 inch / min. The tensile fracture properties of the composite products were measured according to TAPPI method T494. Scissor and tear tests were performed on five strands. ISO whiteness was measured on a Technibrite Micro TB-IC and opacity was measured using a Thwing-Albert Model 323 opacity meter. Opacity, Kubel
Calibrated to 60 g / m ² using the ka-Munk equation. Elongation and TEA were not calibrated to base weight. The composition of each handsheet made for this first example, with some product properties (break length,% elongation and N · m / m ² ), is summarized in Table 2 et seq.

The filter retention was completely satisfactory in most of the tests described by this example, but the addition of small amounts of calcium oxide gave good (80% PCC) retention. Furthermore, no dramatic increase in intensity was observed in this particular example. However, SEM analysis of ash produced by burning handsheets made in accordance with Test T6 shows that such ash retains a composite structure, which is exactly the opposite of the control sample, Indicates that it is unexpected. this is,
It implies fibers that bind in producing an inorganic (mineral) network around fibrous material. In particular, 7 [SEM of handsheet ash derived from handsheet made according to test T6
Image (X 100)] and FIG. 4 [SEM image (X 1000) of handsheet made according to test T6]
It clearly demonstrates that an inorganic (mineral) network is formed. Furthermore, the difference between the composite product of the present invention and the product made by the conventional method is shown in FIGS. 6 and 7 and the control figure 9 [SEM image (X100) of handsheet ash from control handsheet] This is clearly demonstrated by comparing with Control Figure 10 “SEM image of handsheet ash from control handsheet (X1000)”. Figures 9 and 10 show the brittleness characteristic of the ash produced by conventional paper products, while the ash from the composite product T6 clearly maintains an inorganic (mineral) structure even after combustion. I do.

Example 2 This example illustrates one embodiment of a method for making a paper product according to the method of the present invention, and further uses a significantly higher concentration of filler to increase product strength. Prove that you can. The handsheets made according to this example and their components are summarized in Table 2 et seq.

About 30 g (oven dried basis) of fibrous slurry [80% scoured poplar (hardwood)
And 20% scoured bank pine (softwood)] at a concentration of 3.02% in a 2000 ml plastic container. The amounts of precipitated calcium carbonate described in Table 3 (HB PCC from St. Helens)
) And / or calcium oxide (CaOEM. Science GR powder CX0265-3 Lot # 3)
The fibrous slurry was agitated while adding 5222539). Sufficient calcium oxide was added and if completely reacted with carbonic acid, the stated amount of PCC was obtained. After stirring for 5 minutes, sodium silicate solution (sodium silicate solution, National Silicate Ltd. Toronto, Ont
-51.37% oven dried base) was added to all test samples (other than controls).

The sample was carbonated by supplying carbon dioxide to the mixture using a CO ₂ gas cylinder attached to a gas diffusion tube. The carbon dioxide supply was continued for about 2 hours. Since the carbonation step lowers the pH, the time of carbonation is best determined by the pH value. It has been found that the pH of the final target mixture of about 7 to about 8 is sufficient. The carbon dioxide transfer pressure was very low (about 1 psi) and the starting pH was relatively high at about 10-11 (E
M Science colorpHast specimen).

The stock mixture was then diluted to 4 liters and stirred while adding 2% starch. The starch was Hi-Cat 168 cationic potato starch from Rowuette Corp. Thereafter, 0.035% of Percoll 175 (storage aid) was added to the mixture with stirring. The starch step was omitted for the first control, C10.

After the addition of all the materials and the carbonation step were completed, the stirring was stopped to produce a handsheet.
All handsheets were made in Noble & Wood square handsheet molds, wet felt pressed at 20 psi, and dried at 200 ° F in a drum dryer. The target base weight of the handsheet made according to this example was 60 g / m ² . Handsheets were prepared according to TAPPI T222 and tested in the same environment. Tensile tests were performed according to TAPPI T494 at a crosshead speed of 1 inch / min on 7.1 "specimens. ISO whiteness was measured on a Tecnibrite Micro TB-1C and opacity was measured on a Thwing-Albert Model 323 opacity meter. Opacity was corrected to 60 g / m ² base weight using the Kubelka-Munk equation, elongation and TEA were not corrected to base weight. The composition of each handsheet made is summarized below in Table 3. All percentages mentioned in Table 3 are percentages by weight based on oven dried solids of the stock.

[0121] Contrary to expected results, handsheets made according to Example 2 showed increased strength with respect to control sheets at the same ash level. Most interesting is the T13 test. Handsheets formed with the properties described for T13 in Table 3 showed the most dramatic increase in strength. T3 also has the highest silicate content, demonstrating that the formation of the mineral (mineral) network around the fibrous web imparts strength to the final product.

The trend for higher intensity values is shown by comparing T12, T13 and T17. Exam T
17 (3.4% sodium silicate, breaking length = 1.36), T12 (6.4% silicate, breaking length = 1.64km) and T13 (12.1% silicate, breaking length = 1.98km) showed an increase in paper strength. Increasing silicate levels establishes what results from forming a silica / silicate network around the fibrous web. By increasing the silicate concentration from 0% in control C11 with starch to 3.4% for T17, 6.4% for T12 and 12.1% for T13, the breaking length was increased from 1.28 km (C11). 1.36km for T17, 1.6 for T12
4km, increased to 1.98km with respect to T13.

Tests T14, T15 and T16 were made using the same components in the same amounts. In each of these tests, precipitated calcium carbonate was added in addition to calcium oxide and sodium silicate, but the order of addition of the components was different. For the T14 test, all components were carbonated together. For the T15 test, not all of the fibers co-carbonated. T16
For the test, not all, but not all, PCCs were carbonated. Based on the results of these tests, carbonation with PCC, if not all, or carbonation with all, is generally considered to be the best way to form a product according to the present invention.
Furthermore, the fact that the fibers should be present during the carbonation step indicates that the formation of an inorganic (mineral) network around the fibers contributes to the strength enhancement observed in such tests.

FIG. 16 is a graph showing the relationship between the ash content and the breaking length of the handsheets produced according to Example 2. FIG. 16 illustrates that a composite product made according to the invention has a breaking length equal to or greater than a control made with a similar ash content.

Example 3 This example illustrates the formation of an aluminosilicate inorganic (mineral) network around a fibrous material. The method involves using a combination of calcium oxide, sodium silicate, PCC and aluminum sulfide in addition to the cellulosic material. The handsheets made according to this example and their components are summarized in Table 3 et seq. All percentages listed in Table 3 are by weight of the composite based on oven dried solids.

Approximately 30 g (on an oven-dried basis) of a fibrous slurry [80% scoured poplar (hardwood) and 20% scoured pine pine (softwood)] was measured at a concentration of 3.02% in a 2000 ml plastic container. . The amounts of precipitated calcium carbonate (HB PCC from St. Helens), calcium oxide (CaOEM. Science GR powder CX0265-3 lot # 35222539), sodium silicate N solution (National Silivate Limited, Toronto-44.26%) described in Table 3 Oven dried base), aluminum sulfide hydrate (EM Science AX0745-2), cationic potato starch (Hi-Cat 168 from Roquette Corp, batch No.E2845) and Percoll 175 (retention aid from Allied Colloids, batch) While adding No. 2266A), the fiber slurry was stirred.

In Test A-4RD, aluminum sulfide and fibers were mixed together. After stirring for 15 minutes, sodium silicate was added. The calcium oxide and PCC were stirred together for 15 minutes, after which they were added to the fiber, alum and sodium silicate.

In tests C-1P and C-4PD, alum and fiber were mixed together. . After stirring for 15 minutes, calcium oxide and PCC, both of which were also stirred for 15 minutes, were added to the alum and fiber. Sodium silicate was added to the mixture consisting of fiber, alum, PCC and calcium oxide.

In Tests C-4R and C-4RD, alum and fiber were mixed together. After stirring for 15 minutes, calcium oxide (dispersed in water) was added to the alum and fiber. Thereafter, sodium silicate and PCC (both stirred for 15 minutes) were added to the fibers.

In tests S-8R and S-8RD, sodium silicate and fiber were mixed. After stirring for 15 minutes, calcium oxide and PCC, both of which were also stirred for 15 minutes, were added to the sodium silicate and fiber. After that, aluminum sulfide is added to fiber, sodium silicate, PC
C and added to a mixture consisting of calcium oxide. After all of the ingredients were added as indicated above, the stock was diluted to 4 liters and stirred while 2% starch was added.
Thereafter, 0.035% of Percoll 175 was added with stirring. After 2 minutes, stirring was stopped, and handsheets were produced. Controls were similarly prepared, but did not use alum, sodium silicate or calcium oxide. All handsheets are formed on Noble & Wood square handsheet molds, wet felt pressed at 20 psi, and dried in a drum dryer.
Dried to 00 ° F. The target base weight for handsheets made according to this example was 60 g / m ² . Handsheets were prepared with TAPPI T222 and tested in the same environment. Tensile tests were performed by TAPPI method T494 on 7. inch specimens at a crosshead speed of 1 inch / min. ISO whiteness was measured on a Technibrite Micro TB-1C and opacity was measured using a Thwing-Albert Model 323 opacity meter.
Opacity was corrected to 60 g / m ² base weight using the Kubrlka-Munk equation. Elongation and TEA did not correct for base weight. The composition of each handsheet made for this first example is summarized in Table 4 et seq.

Example 3 shows that a composite product was prepared according to the present invention using an aluminosilicate inorganic material.
Prove that it can be manufactured with a (mineral) network structure. Further, the ash versus break length diagram of FIG. 17 further demonstrates that such composite products generally have increased strength properties for products made using conventional methods with equal amounts of ash. .

Example 4 This example further discusses the formation of a composite product using a method similar to that described in Example 1-2. Handsheets made according to this example and their components are summarized in Table 4 et seq. Approximately 30 g of fibrous slurry [80% scoured poplar (hardwood)]
And 20% of scoured bank pine (softwood)] were measured at 3.48% concentration in a 2000 ml plastic container. Thereafter, handsheets were prepared using the conditions described in Table 4. The material used to make the composite product of Table 4 was precipitated calcium carbonate (St. Hel).
HB PCC from ens mill, calcium oxide (CaO EM. Science GR powder CX0265)
−3 lot # 35222539), sodium silicate N solution (The PQ Corp, Valley Forge, PA
; 42.06% oven dried base), cationic potato starch (from Roquette Corp)
Hi-Cat 168, batch # E2845) and Percoll 175 (cation retention aid from Allied Colloids, batch # 2266A). All handsheets of this Example 4 use 2% starch. Test T18 and T1
At 9, calcium oxide and sodium silicate were co-carbonated without fiber. Carbonation was performed through a gas diffusion tube with stirring and at a low CO ₂ transfer pressure of about 1 psi. The starting pH was about 13 (EM Science color pHast indicator test strip) and the sample was carbonated for about 2.5 hours until the pH was about 7. Carbonated sample T-18
And T-19 were stored at room temperature and mixed with the fibers the next day to make handsheets. test
At T-19, PCC and fibrous slurry were added prior to the addition of the carbonated filler. The stock was diluted to 4.5 liters and stirred while adding 2% starch. After stirring for 2 minutes, 0.035% Percoll 175 was added to the stock. Stirring was stopped two minutes after the addition of Percoll to produce handsheets. A similar procedure for adding starch and percoll was used for the following handsheets.

In tests T-20 and T-21, calcium oxide and sodium silicate were added to a pH of about 12
Carbonated with fiber until reduced to about 7. Carbonation time was about 2 hours for T-20 and about 1 hour for T-21. The amounts of calcium oxide and sodium silicate for T-20 were similar to those previously used to make T13, but the lag time between carbonation and handsheet making was different. (1 hour for T-20 and 20 hours for T13). T-21 handsheets were made approximately 3.5 hours after carbonation.

PCC, calcium oxide, and sodium silicate were co-carbonated without fibers in tests T-22, T-23 and T-24 until the pH decreased from about 13 to about 7. Carbonation time was about 1.5 hours. Carbonated samples were stored at room temperature. The amounts of PCC, calcium oxide and sodium silicate for T-22 were the same as previously used for T15, but the lag time between carbonation and handsheet making was different.
(22 hours at T15 versus 5 hours at T-22). All handsheets of this Example 4 were formed on Noble & Wood square handsheet molds, wet felt pressed at 20 psi, and dried at 200 ° F on a drum dryer. The target base weight for handsheets made according to this example was 60 g / m ² . Handsheets were prepared with TAPPI T222 and tested in the same environment.
Tensile tests were performed according to TAPPI method T494 at a crosshead speed of 1 inch / min on 7.1 "specimens. ISO whiteness was measured on a Technibrite Micro TB-1C and measured for Thwing.
-Opacity was measured using an Albert Model 323 opacity meter. Extension and TEA did not correct for base weight.

As described in this Example 4 and Table 5, this result demonstrates that all test samples have increased strength (ie, breaking length) compared to control handsheets. The graph of ash content versus breaking length in FIG. 18 also demonstrates this result. However, it should also be noted that the preferred approach seems to be to form an inorganic (mineral) network in the presence of the fibers. For example, a comparison between T18 and T20 is from 1.36 km for T18 where no fiber is present during the carbonation step to T20 where fiber is present during the carbonation step.
Explain the increase in break length to about 1.88 km.

Test T20 was an attempt to replicate the results of T13. Interestingly, T20 handsheets had a lower ash content (27.6% vs. 33.5%) and lower tensile strength (1.88 vs 1.98km) compared to T13. One major difference between tests T13 and T20 is the processing time, ie, the amount of time allowed to form a mineral (mineral) network. The processing time for T13 was about 20 hours compared to only about 1 hour for T20. It is therefore likely that a higher strength improvement has occurred by increasing the treatment time at least until the formation of the inorganic (mineral) network is substantially completed.

In addition, the results of this Example 4 show that commercially available PCC does not need to be present during the formation of the mineral (mineral) network, and therefore, the carbonation of calcium oxide and sodium silicate. Prove that it does not need to be present during the (oxidation) step.

Example 5 This example discusses the formation of a composite product and further examines cure time, cure temperature, fiber abundance during the carbonation step (0.10 and 100%) and commercially obtained PCC Investigate the effect of the added amount (0 and 50%). The sodium silicate concentration was kept constant at 12.1%, the starch at 2% and the Percoll retention aid at 0.035%. The handsheets made according to this example and their components are summarized in Table 5 et seq.

Approximately 30 g (oven dried base) of fibrous slurry [80% scoured poplar (hardwood)
And 20% refined Banks pine (softwood)] were measured at 2.99% concentration in a 2000 ml plastic container. Thereafter, handsheets were prepared using the conditions described in Table 5. The materials used to make the composite products of Table 5 were precipitated calcium carbonate (St. Hel
HB PCC from ens mill, calcium oxide (CaO EM. Science GR powder CX0265)
−3 lot # 35222539), sodium silicate N solution (The PQ Corp, Valley Forge, PA
; 42.06% oven dried base), cationic potato starch (from Roquette Corp)
Hi-Cat 168, batch # E2845) and Percoll 175 (cation retention aid from Allied Colloids Inc., batch # 2266A).

In Tests T-25, T-26, T-27 and T-28, calcium oxide and sodium silicate were added to a pH of about 12 in the presence of 100% of the fibers used to form the composite product. From about 7 to about 7. Carbonation was performed with low transfer CO ₂ pressure of about 1 psi using a gas diffusion tube with stirring. The carbonated samples were stored at 39 ° F for about 20 hours (T-25 and T-27) to about 42 hours (T-26) before making handsheets. T-2
The eight carbonated samples were stored at about 70 ° F. for about 20 hours before making handsheets.

At T-25 and T-26, all of the PCC was formed by carbonation of the sodium silicate / CaO mixture. In tests T-27 to T-32, half of the final PCC volume was added using commercially available PCC.

In tests T-29 and T-30, 10% of the fiber used to make the composite product
Only was present during the carbonation of the CaO and sodium silicate mixture. The carbonated sample of T-29 was mixed with the remainder of the fiber (90%) and then stored in a refrigerator for about 20 hours before making handsheets. The carbonated sample of T-30 was stored in the refrigerator for about 20 hours before mixing with the rest of the fiber (90%).

In tests T-31 and T-32, calcium oxide and sodium silicate were both carbonated without fiber. About 0.5 hour after carbonation, a handsheet was prepared using the carbonated sample of T-31. The carbonated sample of T-32 was mixed with the fiber and then stored in a refrigerator for about 20 hours before making handsheets.

All handsheets of this Example 5 were formed on a Noble & Wood square handsheet mold, wet felt pressed at 20 psi, and dried at 200 ° F on a drum dryer. The target base weight for handsheets made according to this example was 60 g / m ² . Handsheets were prepared with TAPPI T222 and tested in the same environment.
Tensile tests were performed according to TAPPI method T494 at a crosshead speed of 1 inch / min on 7.1 "specimens. Tensile strength was recorded as the breaking length in km. ISO brightness was Tec
Opacity was measured on a hnibrite Micro TB-1C and opacity was measured using a Thwing-Albert Model 323 opacity meter. Elongation and TEA were not calibrated to base weight.

The graph of ash content vs. break length in FIG. 19 shows that the composite product typically has a longer break length at an equivalent ash content than control handsheets made using conventional methods. Prove that you have. FIG. 20 is a graph of ash content versus breaking length, representing data obtained in Example 2. This graph shows that the composite product made according to the present invention has a silicate content of about 3% to about 12%, has an ash content of 30% or more, and maintains a breaking length of at least 1.4 km. Prove clearly what you have done. The control curve does not even extend to this level of ash content, but it is estimated that the tear length of handsheets made by conventional methods is on the order of only about 0.8 km.

Example 5 also illustrates that treatment time can affect the strength and ash content of cellulosic products made according to the present invention. For example, set the processing time to test T-25
From 22 hours to 42 hours for test T-26. This is 1.75 of T-25
An increase in breaking length from km to 1.95 for T-26 and an increase in ash content from 32.2% for T-25 to 34.8% for T-26 resulted. The formation of an inorganic (mineral) network in the presence of a cellulosic material appears to be an important factor to consider with respect to the formation of a composite product according to the present invention. Test T-29 produced a product by forming an inorganic (mineral) network in the presence of only about 10% fiber. The breaking length of T-29 was about 1.29 km. Inorganic
When the (mineral) network was formed in the presence of 100% fibers as T-27, then the tear length of the handsheet increased to 1.65 km relative to T-29.

Finally, the PCC can be added to the composite product either by formation during the carbonation of the PCC as it is or by the addition of commercially available PCC. Both methods worked, with the slight difference between the T-25 (without PCC, breaking length = 1.75 km) and the T
Compared with -27 (PCC added, breaking length = 1.65km), the strength is seen.

The following example examines the wet tensile strength of paper made by the method of the present invention as compared to a control. Wet tensile strength is an important parameter considered for the production of paper products. Increasing wet tensile strength can provide a significant economic advantage. The following examples clearly demonstrate that paper products made by the method of the present invention have significantly improved wet tensile strength relative to controls.

Example 6 A paper product can be made as described above, where an inorganic (mineral) network is formed in the presence of the cellulosic material. Mg-FLOCC paper and Si-FLOCC paper also
It can be made by at least partially forming an inorganic (mineral) network before adding this material to the cellulose. One advantage of this is that it allows for the continuous formation of paper products.

This example demonstrates the use of an inorganic (mineral) network forming composition for producing Mg-FLOCC paper.
Describe how to make. 345 g sodium silicate (76.3% SiO_Two, 23.7% Na_TwoO2), an aqueous composition consisting of 27.1 g of magnesium oxide and 10 liters of water
Was prepared. 72 g of aluminum sulfide [Al_Two(SO_Four)_Three・ 14-18H_TwoO] or 39 g of Al_Two(SO_Four) ₃ And an aqueous aluminum sulfide mixture consisting of 1 liter of water. The aluminum sulfide mixture was added to the aqueous mixture of sodium silicate and magnesium oxide
. The combined mixture was carbonated with carbon dioxide to obtain a pH of about 7 to about 7.5.

Example 7 This example describes a composition and method for making a Si-FLOCC paper product. An aqueous composition was made up of 265 g of sodium silicate (formed using 76.3% SiO ₂ , 23.7% Na ₂ O) and 10 liters of water. The mixture was carbonated with carbon dioxide to obtain a pH from about 7 to about 7.5.

Example 8 This example compares the wet tensile strength of Ca-FLOCC, Mg-FLOCC, Si-FLOCC handsheets. This example also evaluates the use of PCC to form Ca-FLOCC, Mg-FLOCC and Si-FLOCC handsheets. The wet tensile strength of these handsheets was then compared to control handsheets made in a conventional manner using 12% and 24% PCC fillers.

A control handsheet was made using an organopole retention system. The retention system consists of 0.035% by weight of organopol 21, a non-ionic polymer, and
Contains 0.4% by weight bentonite (Hydrocol O).

Ca-FLOCC, Ma-FLOCC and Si-FLOCC handsheets were prepared as follows. Supply pulp consisting of 75% hardwood and 25% softwood (standard pulp consists of southern market hardwood and softwood refined to 450CSF). This pulp was then mixed with the Mg-FLOCC and Si-FLOCC compositions made as described above in Examples 6 and 7. The filler was then added to the pulp / Ca-FLOCC, Mg-FLOCC and Si-FLOCC compositions as shown in Table 6 et seq. Standard PCC (Albacar LO) was used for PCC-only control paper. An organopole retention system was added to the mixture, after which a handsheet was formed.

A statistical comparison between FLOCC and PCC-only handsheets is given in Table 7 et seq.

1) The change in the press solids is expressed as an absolute value. "-" Indicates a decrease in solids from the PCC only control. 2) Express the change in load peak as a relative%. "+" Indicates an increase over PCC only controls. 3) The same holding system was used for handsheets with FLOCC and PCC only.

Standard test methods were used to determine wet tensile strength and percent solids. Three 61/4 "by1" specimens were produced during paper formation using a mold placed on the forming wire and formed on a Noble and Wood handsheet mold. After the paper is formed, the specimen mold is removed, pressure is applied to the nip, and the paper and wire are pressed between the felt running through a roll press. The test piece was carefully removed, placed in an airtight container and loaded. Tensile measurements were performed using an OPCo wet web tensile tester (Thwing-Albert Ins
trument Co.) at a test interval of 4 seconds and a speed of 0.05 inches / minute. The specimens were dried and the humidity determined, and the remainder of the paper formed was dried for base weight and ash content and loaded to ash.

The Ca-FLOCC, Mg-FLOCC and Si-FLOCC / PCC handsheets and the handsheets with PCC only were almost equivalent in percent solids. The FLOCC-PCC handsheet had a load peak in the wet tensile strength test 15-23% higher than the PCC-only handsheet. Within the context and parameters of this example alone, the best combination of components for paper formation appears to be Ca-FLOCC / PCC handsheets pressed at 70 psi, and this handsheet was PCC pressed at 70 psi. It had 45.4% solids compared to 45.7% solids in the only control and a load peak of 349 units compared to the 228 unit peak in the PCC only control pressed at 70 psi.

FIG. 21 illustrates how the wet tensile strength of a handsheet made as described above changes as the percentage of solids increases. Ca-FLOCC, Mg-FLOCC and Si
-FLOCC handsheets had significantly higher wet tensile strength than the control.

Paper products were made by the method described above using a pilot scale paper machine at the University of West Michigan. The following example describes how these papers were produced.

Example 9 This example describes the formation of a Ca-FLOCC paper. The chemical was carbonated in the presence of fiber using the University of West Michigan hydropulpper as a tube and the slurry was treated for about 24 hours using a holding tank. 480 gallons of water was added to the hydropulper, followed by the careful addition of 100 lbs. Of lime hydroxide {Ca (OH) ₂ }. In previous tests, the procedure of adding water and Ca (OH) 2 was reversed, causing a great deal of surface powdering. Eight minutes after mixing at about 320 rpm, 100 lbs. (OD) of southern softwood pulp and 300 l
bs. (OD) southern hardwood pulp was added. The pulp and calcium hydroxide mixture were mixed for about 30 minutes and mixed at 420 rpm. Then 310 pounds of sodium silicate solution (38.7
Wt% aqueous sodium silicate, 120 lbs. OD solids) into the pulp slurry,
The resulting mixture was mixed for about 30 minutes.

The carbonation of the mixture was started using carbon dioxide gas and solid carbon dioxide (dry ice). The transfer side of the gas conditioner was about 1 psi and the tank side was about 20 psi. Dry ice was added to the pulp and reaction mixture slurry at a rate of about 2 pounds / minute. The slurry had the appearance and properties of dough. The starting pH was about 13. After adding about 175 pounds of dry ice in about 2.5 hours, the pH was 8.85. 4 hours or more after adding gas, dry ice about 25 lb. Later, the slurry pH was about 8.05, while the target pH was 8. Thereafter, the mixture was left to stand overnight. After this treatment step, the pH was 7.55.

[0163] The Ca-FLOCC pulp mixture was then pumped into the mixing chest of a pilot scale paper machine and scoured for the same time and energy used to reach 400 CSF on the untreated pulp blend. Ca-FLOCC paper as a filler from this pulp mixture
Prepared using PCC, ASA as a sizing agent and a retention system consisting of 0.4 lb / ton Percoll 175 (used as 0.1% aqueous solution).

Example 10 This example describes the batch formation of an aluminum-containing Mg-FLOCC and the use of such a material for the production of paper on a test-scale paper machine. Hydropulper from Western Michigan University was used as a container for combining the chemicals used in the Mg-FLOCC process. 500 gallons of water are combined with 10.4 pounds of magnesium oxide (MgO) in a hydropulper and 225 r.
Mix at pm for about 30 minutes. At that time, 344 pounds of sodium silicate (
38.7% by weight aqueous sodium silicate solution; about 133 pounds O.D. D. ) Solution is M
Pumped into a mixture of gO and water. The combination mixture was mixed for 25 minutes.
$ 54 pounds of aluminum sulfate hydrate, which provided $ 29.3 pounds of Al2 (SO4) 3, was dissolved in 40 gallons of water (0.22 g aluminum sulfate / gram silicate). The aluminum sulfate aqueous solution was filtered and added to the above mixture in the hydropulper. After mixing for about 7 minutes, carbonation of the mixture was started using carbon dioxide gas and solid carbon dioxide (dry ice). The initial pH of the mixture is 10.44
Met. Dry ice was added to the mixture at a rate of 1-2 pounds / minute. After 60 minutes, the pH was 7.17 and the addition of dry ice was stopped, but the addition of carbon dioxide gas was continued. 35 pounds of dry ice was added to the reaction mixture. When the pH reached 7.08 after 80 minutes, the addition of carbon dioxide gas was stopped. The target pH was 7. The reaction mixture was mixed with 400 pounds (purified 25/75 S
Pumped against W / HW Northern pulp blend. Mg-FL
The OCC-pulp mixture was then pumped to a blend chest feeding the machine chest. From this pulp mixture, PCC as filler, ASA as sizing agent, and 0.4 lb / ton Organopol 2
Mg-FLOCC paper was prepared using a holding system containing 1 (0.1% aqueous solution) and 8 lb / ton bentonite (Hydrocol O added as a 0.5% aqueous suspension). Was. In these treatments, the retention of the filler was extremely good.

Example 11 This example describes the continuous formation of Mg-FLOCC paper and the use of such material for making paper on a test scale paper machine. 450 gallons of water was combined with 10.4 pounds of magnesium oxide (MgO) in the hydropulper and mixed with the hydropulper screw at 150 rpm for about 20 minutes. Mg
For the mixture of O and water, 338 pounds of sodium silicate (about 131 pounds of OD) solution was pumped, followed by mixing for about 50 minutes. [Providing 29.3 pounds of Al2 (SO4) 3] 54 pounds of aluminum sulfate hydrate was dissolved in about 40 gallons of water, filtered, and added to the reaction mixture in the hydropulper.

After mixing for 5 minutes, carbonation was initiated with carbon dioxide gas (as in Example 10) and solid carbon dioxide (dry ice). The initial pH of the slurry is about 10
. 24. Dry ice was added to the slurry at a rate of about 1-2 pounds / minute. The pH was 7.23 after 65 minutes, and the addition of dry ice was stopped but the addition of carbon dioxide gas was continued. About 35 pounds of dry ice was added to the reaction mixture. After 90 minutes, the addition of carbon dioxide gas was stopped when the pH reached the target pH of 7.00. Gel formation is batch type Mg-F
Darker than LOCC and more equal to the gel observed in the laboratory reaction.

The reaction mixture was pumped into a stirred conical metal container containing a bottom suction hose. This hose was connected to a centrifugal pump. The flow rate from the pump was roughly controlled by a gate valve to about 23.2 pounds / minute or about 2.7 gallons of slurry / minute. This flow rate was less than the calculated value of 3.1 gal / min, which is equivalent to the batch process for making Mg-FLOCC paper. With this system, Mg-FLOC
The C composition was continuously pumped into the drip leg to the fan pump. Good retention was also observed in these treatments. As the process proceeded, the reaction mixture gelled and became thicker, and stirring had to be maintained. After completion of the process, approximately 150 gallons of the 520 gallon Mg-FLOCC reaction mixture remained.

Tables 8-13 below summarize the results obtained for the paper machine trials described above. All listed paper analyzes were performed according to the TAPPI procedure. The amount of carbonate was determined on the ash at 500 ° C. on a CO 2 coulometer to determine the PCC content of the ash, which was within the expected levels. Metal analysis was performed on the acidified sample (hydrochloric acid) with a dielectrically coupled plasma spectrometer. Ca
The sodium content of -FLOCC, Mg-FLOCC and Si-FLOCC was 5 to 10 times that of the control and increased the conductivity of the paper material. This avoids the use of salts in size presses to increase conductivity. Ca-F
The increased sodium content of LOCC, Mg-FLOCC and Si-FLOCC is also evidence that the FLOCC component was incorporated into the paper. SEM micrographs of the paper material prepared as described above were taken (see FIGS. 22 to 27). Table 8 below shows the Ca-FLOCC and Mg-FLO described in Examples 9 to 11.
Provides information on paper machine runs for each of the CC and Si-FLOCC paper stocks.

[0169]

Notes: ^{1 The} holding system used for these trials is indicated as HO
8 lb / ton Hydrocol O and 0.4 lb / ton
Organopol 21 or 0.4 indicated as P
Percol 175 pounds / ton. ² CA refers to, for example, the continuous addition of minerals using the above-described addition equipment. ³ SP Cal-150 refers to the size press and calendering of paper produced by these paper machine processes.

Table 9 provides data on the physical properties of papers made on paper machines as described above in Examples 9-11 in comparison to control papers.

[0172]

Table 10 shows that the paper product produced as described above has little size, since the paper material readily absorbed the applied water. Because. This lack of fineness was addressed in subsequent trial paper machine trials. FIGS. 28 to 31 show the longitudinal (paper direction: machine direction) breaking length for the paper product produced according to the above Examples 9 to 11,
The longitudinal tensile energy absorption (TEA), the transverse TEA, and the rewet breaking length are shown graphically. FIG. 28 demonstrates that the longitudinal tear length for the FLOCC paper product was significantly improved compared to the control ("poly [poly.]" Refers to the polynomial of the line relative to the control data). Conformance). For example, at an ash content of 40%, the longitudinal tear length for Ca-FLOCC paper is equal to that of the control at an ash content of only about 26% ash. At about 32% ash, the Mg-FLOCC paper has a longitudinal tear length equal to that of the control at about 25% ash. At 35% ash, the Si-FLOCC paper has a longitudinal tear length equal to that of the control at about 28% ash.

FIG. 29 shows the longitudinal tensile energy absorption of the FLOCC product made as described above compared to a control. Again, the Ca-FLOCC paper has a significantly improved longitudinal TEA. In particular, Ca-FLOCC is 42% ash,
It has a longitudinal TEA equal to the longitudinal TEA of the control at about 24% ash. Mg-FLOCC and Si-FLOCC papers also have significantly improved longitudinal TEA values as compared to the control. At 35% ash, the Si-FLOCC paper has a TEA equal to the control TEA at about 25% ash, but at about 32%
At ash, Mg-FLOCC has a longitudinal TEA value equal to the longitudinal TEA value of the control at about 26% ash. FIG. 30 for the FLOCC paper compared to the control further embodies the data provided for the longitudinal TEA. In particular, Ca-FLOCC is the best TE
A, and at about 41% ash equals the control CD TEA at about 25% ash. Again, both the Mg-FLOCC proposal Si-FLOCC paper material is significantly better than that of the control.

FIG. 31 shows the longitudinal tear length of the rewet sheet for FLOCC paper compared to the control. This figure dramatically illustrates the significantly better results provided for the FLOCC paper, especially for the Ca-FLOCC process. The highest longitudinal tear length of the rewet sheet for the control was about 340 meters at an ash content of only about 1%. The longitudinal tear length of the rewet sheet relative to the control is from about 340 meters,
The filler amount, therefore, dropped sharply to about 170 meters when the% ash increased to about 16% ash. In contrast, at an ash content of 42%, the longitudinal tear length of the rewet sheet for Ca-FLOCC paper was about 320 meters (i.e., a control with substantially less than 3% filler). Is that of a sheet). Furthermore, Si-
Both the FLOCC and Mg-FLOCC papers also improved significantly over the control. For example, for Mg-FLOCC paper at about 32% ash%, the longitudinal tear length of the rewet sheet is about 210 meters, equivalent to that of the control at an ash content of less than 15% ash. Similarly, the Si-FLOCC paper had a longitudinal tear length of the rewet sheet of about 170 meters at an ash content of 35%, equivalent to that of the control at an ash content of about 20%. An increase in rewet tensile strength is expected for composite products that are strength derived from the mineral network. This therefore supports the unique properties of these products.

Example 12 This example further relates to a test paper machine trial performed on a test paper machine at the University of Western Michigan, Kalamazoo. In these trials, FL
The internal sizing has been significantly increased for the paper product produced by the OCC process. Further, titanium dioxide is added to the cellulose-mineral mixture,
Whiteness and opacity were increased. The pulp for this example was Jackson hardwood pulp. According to fiber analysis of the litter (bale) used in the trial, it was 78-73% hardwood and 2%.
It was shown to be a blend of 2 to 27% softwood. The blend was refined to a 400 bleached kraft hardwood target. St. in a 50 gallon plastic cylinder. HB PCC (about 20% precipitated calcium carbonate) was obtained from the Helens mill.

The holding system was kept constant throughout this trial and
pol 21 and Hydrocol O. The retention system chemistry was supplied by Allied Collides, Suffolk, Virginia. PCC was added as a filler material. Target filler levels for all treatments were 13% to 28%. In an attempt to increase the internal size, ASA / starch emulsions and certain wet end additives were varied. The ASA emulsion used was a 1: 4 ratio of ASA from Cytec to Staley Stalok 400AL.
The size press starch was Staley Ethylex 2040 prepared to 6% solids in a size press. The surface size used in the size press was Cypress 310 from Cytec. Titanium dioxide is TiO2 NA A310 from SCM and was supplied by WMU. Talc is Luze
Mistrofil from Nac America. Polyaluminum chloride (PAC) was PhACSSIZE from Radio Chemical. The zirconium product, Protec ZA7, was from Magnesium Elektron.

All compositions used to make the FLOCC paper stock (composition)
n) and chemicals were the same as described above. The sodium silicate O solution (considered 38.75% solids) was from Havilland Product. Magnesium oxide is available from Martin Marietta Sp.
and the unique Mag Chem 10 was displayed by the companies ecologicals. This powder was cured to a mass and ground before being added to the silicate mixture.
Aluminum sulphate or aluminum sulphate hydrate {Al ₂ (SO ₄ ) ₃ .18H ₂ O, no iron, code 022-1322} was from General Chemical. It is dissolved in water and continuous FLOCC
Used on equipment and wet end. The carbon dioxide was obtained from a liquid Dewar gas branch from Air Products. The gas is a gas heater, a two-stage regulator, a flow meter,
/ 4 inch copper tubing, gas shut-off valve, and then 8 copper gas diffusers (1 inch diameter and 2 inch length, Capstan P
ermaflow) and fed into the reaction mixture. Table 11 below gives the paper machine processing conditions for this example.

[0179]

Notes: ¹ PAC is polyaluminum chloride. ^2. Modified Si-FLOCC by addition of aluminum sulfate. 13% PCC for processes 1-1 to 4-4. 18% PCC for treatment 4-5. 23% PCC for treatments 4-6. 28% PCC for treatment 4-7. 28% PCC for treatments 4-8. 23% PCC for treatment 4-9. 18% PCC for treatment 4-10.

For all treatments, the retention system used was 8 lb / ton Idydro.
col 0 and 0.4 lb / ton Organopol 21.

Notes: ¹ PAC is polyaluminum chloride. * Tested approximately 20 hours after the treatment was completed. Additives were added in a size press to improve the properties of the paper made according to this example. These additives and size press pickups are summarized below in Table 13.

[0183] Table 14 below summarizes the physical properties of the paper product made as described above in Example 13.

[0184]

Si-FLOCC, Mg-FLOCC and Ca-FLOCC paper materials are PCC
It is contemplated that additional fillers, such as those described above and other fillers described above, may also be made. FIGS. 32 and 33 show SEMS of paper materials created by a paper machine.
This shows that the i-FLOCC paper has a PCC filler. When the paper was made on a continuous machine, it was equal to or better than the trial paper on the previous test scale paper machine. The results of these test paper trials are shown in FIGS. FIG. 37 shows a comparison of the paper material characteristics of the PCC-only paper material with respect to the PCC and Si-FLOCC paper materials. This comparison is from the process 3-1 (PCC only) in Table 10, and the next process 3-2 is PCC and Si-FLOCC. As shown, the properties of the FLOCC paper are equal to or better than the low ash PCC only paper. A better comparison is shown in FIG. 38, where the equivalent ash paper material was treated 4
-5 (PCC only) through Process 3-2 (PCC and Si-FLOCC). FIG. 39 shows PCC, titanium dioxide and FLOCC paper (treatment 4-2).
4) is a comparison of the PCC only paper material (processing 4-7) to Figure 4), also showing an improved paper material product.

Example 13 This example relates to a further test paper machine trial performed on a test paper machine at the University of Western Michigan, Kalamazoo. All mixtures and chemicals used to make the Si-FLOCC paper are the same as described above. In this example, the basis weight of the Si-FLOCC and control paper was 36 g /
m ² , but the basis weight of the paper material produced on the test scale paper machine described above in each example was 75 g / m ² . While using 75% hardwood / 25% softwood, 18% PCC filler, _2% TiO 2, 0.4 lb / ton of Organo pol 21,8 lbs / ton Hydrocol 0 and 4 lb / ton ASA An attempt was made to make a control paper material having a size, but this material did not work on the paper machine and 5% PCC was then replaced with a 5% Si-FLOCC mixture, for a total of 13%. PCC was left. It was successfully processed on a paper machine.
The paper making process was more efficient with Si-FLOCC paper. S
The i-FLOCC paper had less breakage than the control and had better release properties. In the first press roll, the control paper adhered to the roll. Si-
The FLOCC paper had significantly better press roll release properties. A substantial reduction in material adhesion to the roll was evidenced by a reduction in material scraped off the press rolls during making the Si-FLOCC paper stock. Si-FLOCC paper material is also created by increasing the TiO ₂ 6.5%. The Si-FLOCC paper had both TAPPI opacity and ISO brightness of 83% to about 85%.

Example 14 This example demonstrates that the processing of pea starch to produce appropriately sized starch particles within a particular particle size distribution allows the treated starch to have a reduced particle size of the filler particles. A method is described that is ready for subsequent use in agglomeration. A micrograph of the pea starch before processing is given in FIG. This should be compared to FIG. 3, which is a photomicrograph of starch after processing as described in this example. The above treatment obviously changes the physical properties of the starch into those of the particles which can be easily identified individually. Although the particles do not have an overall regular shape, the size distribution of the generated particles is sufficiently narrow.

[0188] To a one liter jacketed container, 770 grams of cold water was added. 55 grams of Parrheim's STARLITE pea starch was added to the water by stirring. The starch-water dispersion was stirred until the starch was substantially dispersed, and then the dispersion was heated to 85-90C. The dispersion was maintained at this temperature range for 5 minutes. The dispersion was then allowed to cool to 70 ° C.

Example 15 This example describes a method of treating potato starch to produce an average particle size suitable for subsequent use in agglomerating filler particles. 770 grams of cold water was added to a 1 liter jacketed container. 55 grams of bud potato starch was added to the water by stirring. The starch-water dispersion was stirred until the starch was substantially dispersed, and the dispersion was then heated to 85-90C.
The dispersion was kept within this temperature range for 5 minutes. The dispersion was then allowed to cool to 70 ° C. Starch particles other than pea and potato particles were made in a manner similar to that described above in Examples 1 and 2.

Example 16 This example describes a method of aggregating PCC particles using pea starch treated as described above in Example 1. The micrograph of FIG. 4 shows how the filler particles agglomerated to the pea starch particles when processed as described in the example, and how the pea starch particles It acts as a binder for the. In addition, the size of the floc is determined by the size of the starch particles and not by further processing steps such as exposing the floc to high shear. The ratio of PCC to pea starch for this example was 18: 1. According to Example 1, a 6% by weight aqueous starch dispersion was produced. This steamed (
46.2 grams of cooked pea starch were placed in a 200 milliliter beaker. 46.2 grams of deionized hot water (50 ° C to 70 ° C) was added to the beaker with stirring to form a 3% weight concentration aqueous dispersion. Next, 0.28 grams of polyaluminum chloride, obtained from Radio Chemical, was added to the beaker and vigorous stirring continued to cationize the dispersion.

For a 600 milliliter beaker, 250 grams of a 20% aqueous PCC slurry was added. To the beaker was added 83 grams of warm deionized water (50 ° C to 70 ° C) while stirring using a mechanical stirrer. The stirring speed was then increased. The polyaluminum chloride-starch dispersion was then quickly added to the beaker by vigorous stirring. Vigorous stirring was continued for 10 seconds. This mixing step was also performed using a compounder. After mixing and vigorous stirring, the pre-agglomerated PCC was removed from the handsheet (ha
ndsheet) creation was ready for use.

Example 17 This example describes a method of aggregating PCC particles using potato starch treated as described in Example 2. The ratio of PCC to potato starch for this example was 18: 1.
According to Example 1, a 6% by weight aqueous starch dispersion was produced. 46.2 grams of this cooked pea starch was placed in a 200 milliliter beaker.
46.2 grams of deionized hot water (50 ° C to 70 ° C) was added to the beaker with stirring to form a 3% weight concentration aqueous dispersion. Next, Radio Che
0.28 grams of polyaluminum chloride from Mical was added to the beaker and vigorous stirring continued to cationize the dispersion. For a 600 milliliter beaker, 250 grams of a 20% aqueous PCC slurry was added. To the beaker was added 83 grams of warm deionized water (50 ° C to 70 ° C) while stirring using a mechanical stirrer. The stirring speed was then increased. The polyaluminum chloride-starch dispersion was then quickly added to the beaker by vigorous stirring. Vigorous stirring was continued for 10 seconds. This mixing step was also performed using a compounder. After mixing and vigorous stirring, the pre-agglomerated PCC was ready for use in handsheet making.

Example 18 This example describes a method of making a handsheet using pre-agglomerated filler particles, preagglomerated as described above in Examples 3 and 4. Handsheets were made with a furnish containing 50% bleached kraft hardwood pulp and 50% bleached kraft softwood pulp. Each pulp was separately purified to 560 Canadian Standard Freeness (CSF) by a disc refiner. The pulp was loaded with filler in the range of 15 to 50% of the total furnish (ie, the total amount of pulp and filler). An additive was applied comprising 10 pounds / ton of Stalok cationic starch, 0.5 pounds / ton of Hydrocol 875 cationic polyacrylamide and 2 pounds / ton of Hydrocol 2D5 anionic bentonite. Handsheets were targeted at 1.32 g / sheet, which is equal to 66 g / m ² . Handsheets were made using a standard annular handsheet machine. Agitation, formation and deposition were performed according to TAPPI specification T 205 OM-88. Pressing and drying were not performed according to TAPPI specifications. Instead, press 1
Performed on a platen air press at 82 psi using a foot diameter cylinder.

Five blotters, pre-wetted and pressed and laminated, were used underneath the handsheets and covered on the top with a polished stainless steel plate for 5 minutes. The press moved the handsheets to the plate, which was placed on a 90 ° C. hot water bath until dry. The dried handsheets were placed in the CTH room overnight for physical property testing. All handsheets were tested according to TAPPI test procedure T220 OM-88. Handsheets were made of 50/50 hardwood / softwood fiber furnish. The furnish was combined with PCC to form sheets with 15%, 20%, 30%, 40% and 50% filler loading. Control handsheets were made using PCC slurry. Cationic and anionic materials were used to make the control handsheets, but this is a conventional technique. 10 pounds / ton of Stalok 180 cationic starch, 0.5 pounds of Hydroc to make a control handsheet
ol 875 (cationic polymer) and 2 lb / ton Hydrocol 2
D5 (anionic bentonite) was used.

[0195] No cationic starch was used in making handsheets incorporating the pre-agglomerated filler produced according to the method of the present invention. However, the holding agent is also 0
. 5 pounds of Hydrocol 875 and 2 pounds / ton of Hydroco
l2D5. FIG. 6 shows how the tensile strength in pounds per inch of control handsheets made using PCC and handsheets made according to the example changes with increasing ash content. I have. Although the tensile strength of both handsheets decreased with increasing ash content, the handsheets made according to the example had generally better tensile strength than the control. FIG. 6 further shows that the control has a tensile strength of about 8 at an ash content of about 15%, while the handsheets made according to this example have 25-30%
It has shown that it had the same tensile strength at the ash content of. FIG. 7 shows the control handsheets and the pound / pound of handsheets made according to this example.
It shows how the Murren intensity in inches ² (= psi) changes with increasing ash content. Like the tensile strength, the Murren strength of the two-handed paper decreases with increasing ash content, but the handmade paper made according to this example generally had a better Murren strength than the control. However, Murren strength further dramatically demonstrated the benefits of paper products made in accordance with the present invention. The slope of the line with respect to the control is greater than the handsheets made according to the example, and increasing the amount of filler using the method of the present invention is not as strong as simply increasing the amount of filler. Has a clear effect on Further, FIG. 7 shows that while the control had a Mullen strength of about 11 at an ash content of about 15%, the handsheets made according to this example had the same Mullen strength at an ash content of 25-30%. It is shown that it had. The tensile strength and Mullen strength for handsheets made according to this example are shown in Table 15 below.

[0196]

Example 19 This example describes a method for making a handsheet similar to the one described above. However, for this example, a different retention system, namely cationic starch (Stalo)
k 180) and an anionic polymer (Percol 122LE). For the control handsheet, 30% PCC slurry was 10 lb / ton St
alok 180 and 0.25 lb / ton high molecular weight anionic polymer or Percol 122LE. The same amounts of additives and retention aids were added to the pre-agglomerated PCC. The results obtained in this example are shown in Table 16 below.

[0198]

Tables 15 and 16 and FIGS. 44 and 45 illustrate that paper products made in accordance with the present invention have improved tensile and Murren strength.

Example 20 This example describes a trial scale paper machine trial at the University of Western Michigan. The paper machine was 30 inches wide and had a maximum speed of about 77.8 feet / minute. In these trials, two different starches were used. STALOK3
00 was used as wet end starch and for emulsifying ASA sizing agents. Pea starch was used as described above to pre-agglomerate the filler particles and possibly as an additional additive to STALOK 300 starch. Pea starch was steamed in two different ways. The first was jet steaming as described above, the other was batch steaming at 85-90 ° C and 1 atmosphere.

The pre-agglomeration of the filler particles was such that both the PCC slurry and the pea starch were pumped from separate tanks through a Y-tube into a static in-line mixer. For steamed pea starch, polyaluminum chloride was premixed. The PCC was immediately agglomerated through the static mixer and collected in a tank ready for combination with fiber furnish to make the paper stock. The pulp used in the paper machine trial was 27% kraft softwood and 73%
Bleached craft hardwood. The pulp was refined to 400 CSF. The flocculated filler particles were made with 1 part pea starch with 18 parts PCC and 0.1 part aluminum chloride. STALOK 300 was used as a wet-end starch additive and for dispersing ASA sizing agents.
The amount of STALOK 300 used in trial number 1 shown in FIGS. 8 and 9 and FIG. 16 was 16 pounds / ton and the ASA size amount was 4 pounds / ton. In trial number 2 whose results are shown in FIGS. 10 and 11, only 10
Pounds / ton STALOK was used and ASA was not used. Similarly,
In run # 2, various amounts of pea starch were added at the wet end, which is equal to the amount of pea starch used to pre-agglomerate the PCC. This is shown as PCC slurry + pea starch as described in FIG.

Example 21 This example describes the formation of a Si-FLOCC paper stock containing a pre-agglomerated PCC filler. 28 grams (OD) of 75% / 25% hardwood / softwood from Idaho I
Obtained from international Falls. A mixture useful for making Si-FLOCC paper stock was prepared substantially as described in Example 7.
Forming a 12% aqueous sodium silicate mixture (based on fiber weight);
Thereafter, the mixture was carbonated with carbon dioxide until it gelled, ie for about 5 minutes. The mixture was stirred for about 1.5 hours before further use. The PCC filler was pre-agglomerated with pea starch substantially as described above in Example 14. The pulp was diluted to a 0.4% consistency. Agglomerated PCC was added to the fiber furnish. Thereafter, the gelled mineral network was added to the PCC / fiber furnish mixture. 0.4% bentonite was added based on the weight of the PCC / fiber furnish mixture. This mixture was stirred for about 1 minute.
Next, after 0.035% of Organopol was added, the mixture was stirred for about 30 seconds. From this mixture, a handsheet was made substantially as described above in Example 5.
In addition, a control handsheet was made, containing bentonite and Organopol, but not pre-agglomerated PCC.

Certain properties of handsheets made as described herein above are shown in Table 17 below.

[0204] The invention has been described with reference to the preferred embodiment. Those skilled in the art will appreciate that the invention can be modified from what is described herein within the scope of the following claims.

[Brief description of the drawings]

FIG. 1 is a generalized graph showing percentage ratio of hardwood versus filler content, showing the practical limits of filler content for cellulosic products made using the method developed prior to the present invention. Things. FIG. 2 illustrates the process of silica polymerization. FIG. 3 is a scanning electron micrograph (× 100) of a handsheet manufactured by the Ca-FLOCC method of the present invention. FIG. 4 is a scanning electron micrograph (100 pictures) of a handsheet by the Ca-FLOCC method.
0 times). FIG. 5 is a scanning electron micrograph (× 100) of a handsheet having a PCC manufactured by a conventional method developed before the present invention. FIG. 6 is a scanning electron microscope (× 1000) of a handsheet manufactured by using a conventional PCC developed before the present invention. FIG. 7 is a scanning electron micrograph (× 100) of ash content from hand-drawn (hand-made) paper by Ca-FLOCC. FIG. 8 is a scanning electron micrograph (× 1000) of ash from handsheets by the Ca-FLOCC method. FIG. 9 is a scanning electron micrograph (× 100) of ash from handsheets with PCC, manufactured by conventional methods developed prior to the present invention. FIG. 10 is a scanning electron micrograph (× 1000) of ash from handsheets manufactured using PCC according to a conventional method developed before the present invention. FIG. 11 is a schematic diagram showing a normal papermaking process. FIG. 12 is a block diagram of an apparatus for producing a FLOCC composition according to the method of the present invention. FIG. 13 is a schematic diagram of a commercial embodiment showing an apparatus for continuously producing a FLOCC composition according to the method of the present invention. FIG. 14 is a schematic diagram of a carbonation unit for the apparatus of FIG. FIG. 15 is a cross-sectional view of the carbonation treatment unit of FIG. FIG. 16 is a graph showing the ash content versus the breaking length of the control and composite products made according to the present invention. FIG. 17 is a graph showing the ash content versus the breaking length of a control product and a composite product made according to the present invention. FIG. 18 is a graph showing the ash content versus the breaking length of a control product and a composite product made according to the present invention. FIG. 19 is a graph showing the ash content versus the breaking length of a control product and a composite product made according to the present invention. FIG. 20 is a graph showing the ash content versus the breaking length of a control product and a composite product made according to the present invention. FIG. 21 is a graph showing the percentage of solid content versus peak load indicating wet tensile results. FIG. 22 is a scanning electron micrograph (magnification: 100 ×) of an experimental scale mechanical paper obtained by the Ca-FLOCC method. FIG. 23 is a scanning electron micrograph (× 1000) of an experimental-scale machine-made paper by the Ca-FLOCC method. FIG. 24 is a scanning electron micrograph (magnification: 100 ×) of mechanical scale paper on an experimental scale by the Mg-FLOCC method. FIG. 25 is a scanning electron micrograph (× 1000) of an experimental-scale mechanical paper obtained by the Mg-FLOCC method. FIG. 26 is a scanning electron micrograph (magnification: 150 times) of mechanical scale paper on an experimental scale by the Si-FLOCC method. FIG. 27 is a scanning electron micrograph (2,000-fold magnification) of an experimental-scale mechanical paper obtained by the Si-FLOCC method. FIG. 28 is a graph showing a comparison between the percentage ratio of the ash content and the breaking length in the longitudinal direction. FIG. 29 is a graph showing the percentage of ash content versus longitudinal tensile energy absorption. FIG. 30 is a graph showing the percentage of ash content versus the transverse tensile energy absorption. FIG. 31 is a graph showing the percentage ratio of the ash content to the longitudinal breaking length of the rewet sheet. FIG. 32 is a scanning electron micrograph (× 100) of an experimental-scale mechanical paper obtained by a Si-FLOCC method containing a PCC filler. FIG. 33 is a scanning electron micrograph (× 1000) of an experimental-scale mechanical paper obtained by a Si-FLOCC method containing a PCC filler. FIG. 34 is a graph showing the percentage ratio of the ash content to the longitudinal breaking length of the paper by the Si-FLOCC method. FIG. 35 is a graph showing the percentage ratio of ash content versus the tensile energy absorption in the machine direction for Si-FLOCC paper. FIG. 36 is a graph showing the percentage ratio of the ash content to the longitudinal tear length of the rewet sheet. FIG. 37 shows the paper characteristics of machine-scale paper on an experimental scale using PCC and Si-FLOC.
4 is a bar graph showing the paper properties of an experimental scale machined paper by Method C at different ash contents. FIG. 38 shows the paper characteristics of machine-scale paper on an experimental scale using PCC and the Si-FLOC.
4 is a bar graph showing the paper properties of an experimental scale machined paper by the C method with equivalent ash content. FIG. 39 shows a comparison between the paper properties of an experimental-scale machined paper using PCC and the paper properties of an experimental-scale machined paper obtained by the Si-FLOCC method containing PCC and titanium dioxide. It is a bar graph shown by content. FIG. 40 is an optical micrograph of pea starch (pea starch) before treatment according to the present invention. FIG. 41 is an optical micrograph of the pea starch granules treated according to the present invention, with a 100 μm long indicator rod. FIG. 42 is an optical micrograph showing PCC filler particles agglomerated into starch granules following treatment according to the present invention, with a 100 μm long indicator rod. FIG. 43 shows how the viscosity of an aqueous dispersion of starch changes with increasing temperature. FIG. 44 shows how the tensile strength of handsheets produced by the method of the present invention and the control handsheet changes with increasing ash content. FIG. 45 shows how the Murren strength of handsheets produced by the method of the present invention and the control handsheet changes with increasing ash content. FIG. 46 shows how the breaking length of the experimental machine of the paper produced by the method of the invention and the control paper changes with increasing ash content. FIG. 47 shows how the sizing for paper made by the method of the present invention and control paper changes with increasing ash content. FIG. 48 shows whether the experimental mechanical rupture length for paper made by the method of the present invention and control paper changes as the ash content increases. FIG. 49 shows how the opacity of the experimental mechanical paper produced by the method of the present invention and the control experimental mechanical paper changes with increasing ash content.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) D21H 23/04 D21H 17:67 23/76 D06M 11/12 // D21H 17:67 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI) , CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, K, EE, ES, FI, GB, GE, GH, GM, HR, HU, ID, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG , UZ, VN, YU, ZW (72) Inventor Mike SD Chuning, Washington, USA 98686 Vancouver North East One Hundred Fifteens Street 3319 (72) Inventor Larry El Malcolm United States of America 98671 Washogar South East Sunset View Road 36839 (72) Inventor James S. Johnson 97214 Portola, Oregon United States De South East Thirty Seventh Avenue 1829 (72) Inventor David Tee Lee United States of America 98665 Washington DC 800665 (72) Inventor Barbara Earl Asa United States of America 98682 Vancouver North East Na Inti Six Street 15219

Claims (63)

[Claims] 1. A cellulosic product comprising a cellulosic material and an inorganic network formed around the cellulosic material. 2. The product according to claim 1, comprising a paper product. 3. The article of claim 1, wherein said inorganic network comprises a silica / silicate network. 4. The product of claim 1, wherein the ash produced from the product is similar to the scanning electron micrographs of FIGS. 7 and 8. 5. The product of claim 1, wherein the product comprises Ca-FLOCC paper. 6. The product of claim 1, wherein the product is made of Mg-FLOCC paper. 7. The product of claim 1, wherein the product comprises Si-FLOCC paper. 8. The product of claim 1, wherein the product has an ash content of at least 30% and a longitudinal tear length of at least about 2500 meters. 9. The product of claim 1, wherein the product has an ash content of at least 35% and a longitudinal tear length of about 2500 meters or more. 10. The product of claim 1, having an ash content of at least 25% and a longitudinal TEA of 1 ft · lb / ft ² or greater. 11. The product of claim 1 having an ash content of at least 30% and a longitudinal TEA of 1 ft · lb / ft ² or greater. 12. The product according to claim 1, wherein the rewet sheet has a longitudinal tear length of at least 175 m with an ash content of at least 25%. 13. The product according to claim 1, wherein the longitudinal tear length of the rewet sheet is at least 20 m with an ash content of at least 25%. 14. The product of claim 1, wherein the rewet sheet has a longitudinal tear length of at least 20 m with an ash content of at least 30%. 15. The product according to claim 1, wherein the rewet sheet has a longitudinal tear length of at least 20 m with an ash content of at least 35%. 16. A cellulosic paper product comprising a cellulosic fiber material and a silica / silicate network formed around the cellulosic fiber material. 17. A method for producing a cellulose product, comprising preparing a cellulose fraction and forming an inorganic network around the cellulose fraction. 18. A mixture comprising a cellulosic material, a Group I metal silicate, and a Group II metal base or salt in producing the inorganic network is provided, wherein the mixture is treated with about 7 to about 8 18. Carbonating for a period of time sufficient to obtain a pH of the cellulosic product comprising a precipitated carbonate filler material and a polymerized inorganic network around the cellulosic material. The described method. 19. The method of claim 1, wherein said Group I metal silicate is sodium silicate.
8. The method according to 8. 20. The method of claim 18, wherein said Group II metal base is CaO and said precipitated carbonate filler is calcium carbonate. 21. The method according to claim 18, wherein carbonating the mixture comprises mixing the mixture with carbon dioxide. 22. A method of making a paper product, comprising from about 40% to about 60% of a cellulosic material, from about 1% to about 20% of a Group I metal silicate, and from about 1% to about 45%. % Of a Group II metal base or salt, and the mixture is carbonated to form a precipitated carbonate filler and an inorganic network polymerized around said cellulosic material. A method for producing a paper product, wherein the mixture is formed into a paper product. 23. The mixture by further adding a material selected from the group consisting of precipitated calcium carbonate, retention aids, whitening agents, insecticides, sizing agents, starch, other fillers, pigments and mixtures thereof. 23. The method according to claim 22, wherein 24. The method of claim 22, wherein carbonating the mixture comprises mixing the mixture with carbon dioxide. 25. The Group I metal silicate is sodium silicate.
2. The method according to 2. 26. The method of claim 22, wherein said Group II metal base or salt is a calcium base or salt. 27. The method of claim 24, wherein said Group II metal base or salt is a calcium salt. 28. A method of making a paper product, comprising about 40% to about 60% cellulosic material, about 1% to about 20% sodium silicate, and about 1% to about 45% CaO. Forming a mixture and carbonating the mixture with CO2 to form a precipitated calcium carbonate filler material and a silica / calcium silicate network polymerized around the cellulosic material; A method of manufacturing a paper product by molding into a paper product. 29. A product made by the method of claim 17. 30. An article made by the method of claim 22. 31. An article made by the method of claim 28. 32. A method of pre-agglomerating filler particles useful in the manufacture of paper products, comprising the steps of: providing a starch, treating the starch to produce starch granules, and converting the adjuvant particles to the starch granules. To form a filler particle-starch agglomerate by mixing. 33. The method of claim 32, wherein said starch is selected from the group consisting of legume starch, potato starch, corn starch, and mixtures thereof. 34. The method of claim 32, wherein said starch is pea starch. 35. The method of claim 32, wherein said starch is potato starch. 36. The process of treating a starch, wherein an aqueous dispersion of starch is formed, and the dispersion is heated at a temperature and for a time sufficient to form starch granules. 32. The method of claim 32. 37. The method of claim 36, wherein in the step of forming the aqueous dispersion of starch, the starch is added to cold water to form a dispersion containing from about 1 to about 10% starch by weight. Method. 38. The method of claim 36, wherein in the step of forming the aqueous dispersion of starch, the starch is added to cold water to form a dispersion containing from about 5 to about 7% by weight of starch. Method. 39. The method of claim 36, wherein heating the dispersion comprises heating the dispersion to a temperature from about 60 ° C to about 120 ° C. 40. The method of claim 36, wherein heating the dispersion comprises heating the dispersion to a temperature of about 80 ° C. to about 90 ° C. 41. The method of claim 32, wherein the average particle size of the starch granules is from 15 μm to about 150 μm. 42. The method of claim 32, wherein said starch granules have an average particle size of from 40 μm to about 70 μm. 43. The method of claim 32, wherein said starch granules have an average particle size of 50 μm to about 60 μm. 44. The method of claim 32, wherein said starch is an unmodified starch. 45. The group of the filler particles comprising aluminum sulfate, ground calcium carbonate, chalk, clay, titanium dioxide, talc, dolomite, calcium sulfate, barium sulfate, kaolin, aluminum hydroxide, satin white and mixtures thereof. 33. The method of claim 32, wherein the method is selected from: 46. The starch is pea starch, wherein the pea starch comprises about 4
33. The method of claim 32, wherein the filler material is fine granules having an average particle size of 0 to about 70 m, and wherein the filler material comprises calcium carbonate. 47. A method of making a paper product, comprising: providing a starch selected from the group consisting of legume starch, potato starch, corn starch and mixtures thereof, treating the starch to produce starch granules. A method of manufacturing a paper product, comprising: forming a filler particle-starch agglomerate by mixing filler particles with the starch granules; and combining the agglomerate with a cellulose furnish to form a paper product. 48. In treating the starch, an aqueous starch dispersion containing about 1% to about 10% starch by weight is formed, and the dispersion is treated at a temperature of about 60 ° C. to about 120 ° C. Heating for a time sufficient to produce starch granules having a particle size in the range of about 40 μm to about 70 μm;
50. The method of claim 47. 49. The method of claim 47, wherein said starch is pea starch. 50. The method of claim 47, wherein said starch is potato starch. 51. The method of claim 47, wherein forming the aqueous dispersion of starch comprises adding starch to cold water to form a dispersion containing about 5 to about 7% starch by weight. Method. 52. The method of claim 48, wherein heating the dispersion comprises heating the dispersion at a temperature from about 80 ° C. to about 90 ° C. 53. The method of claim 47, wherein said starch granules have a particle size in a range from about 50 μm to about 60 μm. 54. The group wherein the filler particles comprise aluminum sulfate, ground calcium carbonate, chalk, clay, titanium dioxide, talc, dolomite, calcium sulfate, barium sulfate, kaolin, aluminum hydroxide, satin white and mixtures thereof. 48. The method of claim 47, wherein the method is selected from: 55. A method of making a paper product, comprising: preparing pea starch; adding the pea starch to cold water to produce an aqueous dispersion of pea starch, wherein the dispersion comprises from about 1% to about 10% by weight. And heating the dispersion at a temperature of about 70 ° C. to about 90 ° C. for a time sufficient to produce starch granules having a particle size in the range of about 40 μm to about 70 μm. A cationizing agent is added to the aqueous dispersion, and a filler particle-starch aggregate is formed by mixing the auxiliary particles with the starch fine particles. Calcium, chalk, clay, titanium dioxide, talc, dolomite, calcium sulfate,
Selected from the group consisting of barium sulfate, kaolin, aluminum hydroxide, satin white and mixtures thereof, wherein the filler particles-starch fines aggregates are combined with a cellulose furnish to produce a paper product; Manufacturing method of paper products. 56. The method of claim 55, wherein in the step of forming the aqueous dispersion of pea starch, a dispersion containing about 5 to about 7% starch by weight is added by adding the pea starch to cold water. Method. 57. The method of claim 55, wherein heating the dispersion comprises heating the dispersion to a temperature of about 80 ° C. to about 90 ° C. 58. The method of claim 55, wherein the average particle size of the starch granules is from about 50 μm to about 60 μm. 59. A paper product made by the method of claim 32. 60. A paper product produced by the method of claim 47. 61. A paper product produced by the method of claim 55. 62. A paper product comprising a cellulosic material and pea starch granules and agglomerated filler particles. 63. A method of making a paper product, the method comprising treating starch to produce starch granules, and mixing the filler particles useful for making a paper product with the starch granules. By pre-aggregating the filler particles by forming an aggregate of starch and starch, preparing a cellulose fraction, simultaneously with binding the aggregate of the filler particles and starch to the cellulose fraction, or A method for producing a paper product, wherein an aggregate of the filler particles and starch is combined with the cellulose fraction, and then an inorganic network structure is formed around the cellulose fraction.